GLASS PRODUCT WITH BRAND AND PREPARATION PROCESS

Abstract

A process for preparing a branded glass product and the branded glass product obtained according to the process. The process comprises: 1) coating a glass substrate surface with an ink composition; 2) heating the glass substrate obtained in step 1); and the branded glass product, where the ink contains particles having a size of 150 to 600 nm, preferably 150 to 350 nm, and more preferably 200 to 300 nm. The ink composition is also used in the process for preparing the branded glass product.

Description

The present invention relates to the field of marking glass products, in particular, to a glass product with the mark and the process of preparing the same. BACKGROUND OF THE INVENTION As more emphasis is placed on product quality, tracking product information—such as the production process, manufacturers, and logistics—is becoming increasingly popular to facilitate big data analysis. By placing a mark on a glass product, such as a two-dimensional code or barcode, information about each glass product, including its production process, manufacturer, logistics, and so on, can be traced by reading the mark, enabling a rapid response. At the same time, the marking can also play a role in anti-counterfeiting identification. To ensure legibility, the integrity of the mark must be maintained during subsequent processing steps of the glass product and after prolonged use; that is, the mark needs to have good wear resistance and weather resistance. In the prior art, although inkjet printing using mineral-based ink / enamel can have a certain degree of heat resistance, it is difficult to maintain the mark's integrity during the glass cleaning process. A mark produced by laser transfer technology using enamel-based ink on glass can be retained during glass processing steps, such as cleaning and heating, and the mark's color integrity can also be maintained. The mark also possesses some degree of wear resistance and weather resistance.However, non-integrated printheads are more expensive, which reduces their applicability. Inkjet printing using a special high-temperature resistant ink (UV-polymerized ink or hot-dry ink) allows markings to be made on glass. For example, EP3365398A1 describes a UV-curable frit-based inkjet ink composition comprising a glass frit component, a chromophore component, and a UV-curable component, which is used to coat glass, ceramic, or metal using an inkjet printer. However, the color of the marks obtained using a high-temperature resistant ink is generally undesirable, for example, brown. This is unsatisfactory for users with high aesthetic requirements for glass products. For glass products, an invisible / near-invisible mark is often used for aesthetic reasons. This mark is frequently achieved using a UV-type ink. For example, CN103666057A describes a UV-curable invisible fluorescent ink. However, most UV-fluorescent molecules are not resistant to high temperatures, making it difficult for the mark to withstand high-temperature processing, such as shaping glass during manufacturing. Furthermore, the fluorescent component of the UV mineral is usually a rare-earth element-based doped substance, resulting in low conversion efficiency and high cost. ML / a / zuzi / ui uo iy Therefore, given the challenges in the prior art, a suitable marking system for glass products remains essential. This marking must not only provide relevant information for product traceability but also be wear-resistant and weather-resistant. According to current requirements, the marking must be either visible or invisible to the naked eye. Ideally, the marking should be "invisible" or "stealthy" to users but machine-readable, enabling traceability without detracting from the glass's appearance. Similarly, a process for obtaining a branded glass product is desirable in the state of the art. BRIEF DESCRIPTION OF THE INVENTION According to the first aspect of the present invention, a process is provided for preparing a marked glass product, wherein the process comprises 1) coating an ink composition onto a glass substrate surface, 2) heating the glass substrate obtained in step 1); wherein, in the marked glass product, the mark contains particles having a size with a lower limit of 150 nm or more, preferably 200 nm or more; the particles have a size with an upper limit of 600 nm or less, preferably 350 nm or less, more preferably 300 nm or less. In one form, the particles are crystals. In another modality, the ink composition comprises a compound containing a halogen and / or a phosphate-based compound. In a preferred embodiment, based on the total weight of the ink composition, the lower limit of the content of the halogen-containing compound is 0.5% by weight or more, preferably 1% by weight or more; the upper limit of the content of the halogen-containing compound is 10% by weight or less, preferably 5% by weight or less; and / or the lower limit of the content of the element phosphorus in the phosphate-based compound is 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.15% by weight or more; the upper limit of the content of the element phosphorus in the phosphate-based compound is 4% by weight or less, preferably 3% by weight or less, more preferably 2.5% by weight or less. In one embodiment, a glass substrate processing step is included before step 1), where the preprocessing step comprises a cleaning step. In one modality, the coating in step 1) is done with inkjet printing. In one embodiment, the lower limit of the thickness of the ink composition coated on the surface of the glass substrate in step 1) is 1 pm or more; the upper limit of the thickness is 100 pm or less, preferably 60 pm or less, most preferably 35 pm or less. In one modality, the heating in step 2) is carried out at a temperature of 550 to 750°C. According to the second aspect of the present invention, a glass product with the mark prepared according to the process of the first aspect of the present invention is provided. According to the third aspect of the present invention, a glass product is provided with the mark, wherein the mark contains particles having a size with a lower limit of 150 nm or more, preferably 200 nm or more; with an upper limit of 600 nm or less, preferably 350 nm or less, more preferably 300 nm or less. In one form, the particles are crystals. In one embodiment, at least a portion of the mark is present beneath a glass substrate surface and extends along the thickness direction of the glass substrate from the glass substrate surface to the interior. In one embodiment, in the glass product with the mark according to the second aspect or the third aspect of the present invention, the mark is visible or invisible to the naked eye in transmission according to current requirements. In a preferred embodiment, in the glass product with the mark according to the second aspect or the third aspect of the present invention, the mark is invisible to the naked eye in transmission. In a preferred embodiment, in the glass product with the mark according to the second aspect or the third aspect of the present invention, the mark is invisible to the naked eye in daylight or reflected natural light. In one embodiment, in the glass product with the mark according to the second aspect or the third aspect of the present invention, the mark is legible in the following light source: the spectral peak of the light source located in the blue light and / or UV light. In a preferred embodiment, on the glass product bearing the mark according to the second aspect or the third aspect of the present invention, the mark is legible in Neon light, cool white LED light, blue light, UV light, or collimated reflected light. In one embodiment, in the glass product with the mark according to the second aspect or the third aspect of the present invention, the lower limit of the depth of the mark extending along the thickness direction of the glass substrate from the surface of the glass substrate to the interior is 5 nm or more, preferably 10 nm or more; the upper limit of depth is 100 pm or less, preferably 50 pm or less, more preferably 10 pm or less. In one embodiment, in the glass product with the mark according to the second aspect or the third aspect of the present invention, the mark is an identification code, for example, a Data Matrix code, a two-dimensional code, a QR code, or a barcode. In one embodiment, the glass product bearing the mark according to the third aspect of the present invention is prepared according to the process for preparing the glass product bearing the mark of the first aspect of the present invention. According to the fourth aspect of the present invention, the use of an ink composition is provided in the process for preparing a marked glass product according to the first aspect of the present invention or in the preparation of the marked glass product according to the second or third aspect of the present invention, wherein the mark contains particles having a size with a lower limit of 150 nm or more, preferably 200 nm or more; with an upper limit of 600 nm or less, preferably 350 nm or less, more preferably 300 nm or less. In one form, the particles are crystals. In another modality, the ink composition comprises a compound containing a halogen and / or a phosphate-based compound. In a preferred embodiment, based on the total weight of the ink composition, the lower limit of the halogen-containing compound content is 0.5% by weight or more, preferably 1% by weight or more; the upper limit of the halogen-containing compound content is 10% by weight or less, preferably 5% by weight or less; and / or the lower limit of the phosphorus element content in the phosphate-based compound is 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.15% by weight or more; the upper limit of the phosphorus element content in the phosphate-based compound is 4% by weight or less, preferably 3% by weight or less, more preferably 2.5% by weight or less. Beneficial Effect The glass product bearing the mark of the present invention does not have the problem of ink adhesion or enamel adhesion. Furthermore, since the marking of the present invention is partially present beneath the surface of the glass, it can withstand subsequent processing steps of the glass product and retain its integrity, even after prolonged use. Therefore, the marking on the glass product of the present invention has good wear resistance and weather resistance. According to current requirements, the mark of this document may be visible or invisible to the naked eye. In a preferred embodiment, the mark of the present invention is invisible to the naked eye in transmitted light and is also invisible to the naked eye in daylight or natural light in reflected light. Therefore, the mark of the present invention can achieve the tracking function without aesthetically affecting the appearance of the glass. The glass product with the mark according to the invention has enhanced aesthetics, which can satisfy the aesthetic requirements of customers in everyday life. Furthermore, the mark of the present invention remains legible under the following light sources: the spectral peak of the light source located in the blue and / or UV range. For example, the mark is legible under neon light, cool white LED light, blue light, UV light, or collimated reflected light. Therefore, the mark of the present invention can be read to obtain information about the glass product, such as the production process, manufacturer, logistics, and the like, thus enabling the product to be traced and facilitating a rapid response. The process for preparing a branded glass product has a simple preparation process, is low cost and is suitable for large-scale industrialized production. BRIEF DESCRIPTION OF THE FIGURES Figure 1a: Schematic diagram of the D65 light source. Figure 1b: Cool white LED light spectrum. Figure 2: Schematic diagram of one modality of a process for preparing a branded glass product. MA / a / zuz i / ui uoi a Figures 3a and 3b: the image of the portion of the glass product brand with the Example 1 brand presented in Figure 3a UV light and dark field, Figure 3b collimated light of 4000 lux. Figure 4: SEM image of the portion of the glass product brand with the Example 2 brand. Figure 5: Microscopic image of the portion of the glass product mark with the mark in the dark field of Example 2. DETAILED DESCRIPTION OF THE INVENTION The implementation and application of the modalities are discussed in detail below. It should be understood, however, that the specific modalities discussed merely illustrate specific ways of implementing and applying the present invention and do not imitate the scope of the present invention. Definitions and general terms The invention will now be further described in detail below and it should be understood that the terms are for the purpose of description, but are not intended to limit the invention. The technical and scientific terms used herein have the same meaning as commonly understood by a person skilled in the prior art to which this invention belongs, unless otherwise indicated. In case of conflict, the definition provided in this application shall prevail. When a certain quantity, concentration, or other value or parameter is expressed in the form of a range, a preferred range, a preferred upper numerical limit, and a preferred lower numerical limit, it shall be understood that any range combining any of the upper or preferred value of the range with any lower or preferred value of the range is specifically cited, regardless of whether the range is specifically described.The intervals of values ​​quoted herein are intended to include the interval endpoints and all whole numbers and fractions (fractions) within the interval, unless otherwise stated. The terms “around” and “approximately” when used in conjunction with a numerical variable generally refer to the values ​​of the variable and all values ​​of the variable within the experimental error (e.g., within a 95% confidence interval of the mean) or within ±10% or wider of the specified value. The term “optional” or “optionally” as used herein means that the event or circumstance described below may or may not occur. The description includes the occurrence or non-occurrence of the event or circumstance, as well as the arbitrary selection of the content described below. Unless otherwise stated, percentages, parts and the like herein are provided by weight. The expressions “including,” “comprising,” “having,” “containing,” and similar terms have an inclusive meaning and do not exclude additional unlisted elements, steps, or components. The expression “consisting of” excludes any element, step, or ingredient not specified. The expression “consisting essentially of” means that the scope is limited to the specified elements, steps, or components, along with any elements, steps, or components that are optionally present and do not substantially affect the basic and novel characteristics of the claimed subject matter. It should be understood that the expression “comprising” encompasses the expressions “consisting essentially of” and “consisting of.” The term “one or more” or “at least one”, as used herein, means one, two, three, four, five, six, seven, eight or more. In this context, “external” and “internal” are directions with respect to the vehicle body; “external” refers to a direction away from the vehicle body and “internal” refers to a direction oriented towards the vehicle body. In this context, the term “not high-temperature resistant” for the ink composition means that a generally accepted ink composition would not be able to withstand temperatures of 500°C to 800°C, 550°C to 750°C, and higher. The ink composition might not retain its original shape, color, or other physical properties at these temperatures, as it would decompose, char, or burn to ash. In this context, the term “mark” can be a symbol, a figure, an identification code, or any pattern; for example, it can be an identification code. Identification codes include, but are not limited to, barcodes, two-dimensional codes, Data Matrix codes, QR codes, or those mentioned in CN106061746A, such as 3-DI Code, Aztex Code, Codablock, Code 1, Code 16K, Dot Code, ezCode, BeeTagg Big, BeeTagg Landscape, Maxicode, Snpwflake, Verocode, BeeTagg Hexagon, BeeTagg None, ShotCode, MiniCode, Code 49, Datastrip Code, CP Code, and ISS SuperCode. In this context, the term “ink” can also be called writing ink. In this context, the term “collimated light” can also be called parallel light. In this context, the term “cool white LED” refers to the characteristics of a cool white LED commonly used in the prior art. Specifically, its spectral characteristic is high in the blue portion and low in the green portion, with the highest peak in the blue portion of the spectrum. For example, the intensity of the blue light is approximately 3.33 times that of the green light, and the energy of the blue light is approximately 4.5 times that of the green light. The intensity of the cool white LED in the blue portion is greater than that of a D65 light source. In natural or daylight conditions, the intensity of the blue light is less than that of the green light (for example, approximately 0.68 times), and the energy of the blue light is less than that of the green light (for example, approximately 0.9 times).Figures 1a and 1b show a schematic diagram of the spectra of a D65 light source (the most commonly used artificial daylight in standard light sources, with a color temperature of 6500K) and cool white LED light. It can be clearly seen that the cool white LED light has a relatively high intensity in the 400–480 nm wavelength range. The spectral peak of the cool white LED light is between 400 and 480 nm. The color difference value used herein, i.e., ΔE (Delta-E), refers to a test unit for the difference in color perceived by the human eye in a uniform color perception space. ΔE can be calculated based on the following formula: where, L* refers to the brilliance of the glass with the marked portion; ΔE = J(L' - UrefY + {a* - + (b* - b;efy a* refers to the red-green color of the glass with the marked portion; b* refers to the blue-yellow color of the glass with the marked portion; L*ret, a*ref, b*ref refers to the corresponding values ​​of the glass without the marked portion (control glass). The ΔE is measured using a color difference meter, for example, the Minolta color difference meter. The test light source is, for example, a visible light source, such as the D65 light source. The color difference between the marked and unmarked portions can be characterized by the ΔE. In this context, “the spectral peak of the light source is located in the blue and / or UV light” generally refers to a light source with a spectral peak located in the range of 100 to 480 nm, preferably Neon light, cool white LED light, blue light, UV light, collimated light or a combination thereof, most preferably blue light and / or UV light. In this context, ultraviolet light is also called UV light, with the wavelength range usually around 400 nm or less, for example, around 100 to 400 nm. In this context, blue light has a wavelength of around 400 to 480 nm. In this context, the wavelength of visible light is generally around 380 to 780 nm, preferably 400 to 780 nm. In this context, the term “visible to the naked eye” has a commonly understood meaning within the prior art. Specifically, the marked portion is different from the unmarked portion when observed with the naked eye. Therefore, the mark can be observed with the naked eye. In this context, the term “invisible to the naked eye” is also called “stealth,” which has a commonly understood meaning in the prior art. Specifically, there is no significant difference in transmissibility between the marked and unmarked portions of the product, meaning the mark cannot be observed with the naked eye. The irradiation light source can be, for example, visible light, daylight, natural light, ambient light, LED light, blue light, and similar. In one modality, there is almost no difference in transmissivity between the marked and unmarked portions. In another modality, when a glass product with the mark is tested using a D65 light source, the color difference (ΔΕη) value of the marked portion compared to the unmarked portion is approximately 0.5 or less, for example, approximately 0.4, 0.2, or close to 0.In one further embodiment, the mark is also invisible to the naked eye in daylight, natural light, visible light, or reflected ambient light. In yet another embodiment, when a glass product bearing the mark is tested using a D65 light source, the color difference (ΔΕη) value of the marked portion compared to the unmarked portion in reflection is approximately 3 or less, for example, from approximately 0.85 to 2, for example, 0.9 to 1.5. In this context, the term “legible” can also be called “identifiable,” which has a commonly understood meaning in the prior art. “Legible” or “identifiable” refers to the fact that a mark can be captured in a clear image by a reading device and read to convert it into information corresponding to the mark. In this context, the term “reading device” may also be called an “identification scanner,” which is a reading device commonly understood in the prior art. A reading device generally contains a light source, a lens, a light-sensitive element, and a decoding element that can convert light signals into electrical and similar signals. In one embodiment, the light source of a reading device is generally a light source whose spectral peak is located in the blue and / or UV light portion, i.e., a light source whose spectral peak is located from 100 to 480 nm. In a preferred embodiment, the light source is neon light, cool white LED light, blue light, UV light, collimated light, or a combination thereof. The reading device may be, for example, an identification scanner from Cognex or Keyence. In this context, the term “halogen” refers to fluorine, chlorine, bromine, iodine. In this context, the term “surface roughness” has a commonly understood meaning in the prior art, referring to a machined surface with minimal peak and valley variations. Characterization can be performed using a comparison method, contact style method, light sectioning method, interference method, or similar method. For example, measurement could be carried out with a surface roughness measuring instrument, a profilometer, or a surface profilometer, such as the Bruker Dektak Profilometer. Preparation Process A process is provided for preparing a branded glass product, wherein the process comprises: 1) to coat an ink composition onto a glass substrate surface, 2) Heat the glass substrate obtained in step 1). In one embodiment, in the branded glass product, the brand contains particles with a lower size limit of 150 nm or more, preferably 200 nm or more; and the particles have an upper size limit of 600 nm or less, preferably 350 nm or less, most preferably 300 nm or less. The particles may exist in one or more of the following locations: partially interspersed within the glass substrate where the brand is located, arranged on the surface of the glass substrate where the brand is located, and embedded within the glass substrate where the brand is located. In preferred embodiments, the particles are crystals. In one embodiment, a preprocessing step of the glass substrate is included before step 1), where the preprocessing step comprises a cleaning step. The cleaning may maintain the surface of the glass substrate clean to remove organic or inorganic contaminants that may be present on the surface of the glass substrate, for example, those left during the preparation process of the glass substrate. In one embodiment, the cleaning is carried out by brushing to remove contaminants from the surface of the glass substrate. In another embodiment, the cleaning is carried out by polishing or grinding to remove contaminants from the surface of the glass substrate. Μλ / a / zuzi / ui uo iy In step 1), an ink composition is coated onto the surface of the glass substrate, as shown in Figure 2. The method of coating the ink onto the glass substrate surface must ensure that the ink adheres uniformly to a predetermined position on the substrate. The coating can be achieved by printing, which includes, but is not limited to, screen printing or inkjet printing. Inkjet printing is preferred. Inkjet printing utilizes a method commonly employed in the prior art, for example, an inkjet printer such as the Markem-lmaje 9450 inkjet printer. The printer configurations are conventional in the prior art. In one embodiment, the amount of ink composition coated onto the surface of the glass substrate must be appropriate so that a legible "invisible mark" effect can be achieved. In one embodiment, the amount of ink composition coated onto the surface of the glass substrate is expressed by the thickness of the ink composition. The lower limit of the ink composition thickness is 1 µm or more; the upper limit of the thickness is 100 µm or less, preferably 60 µm or less, and more preferably 35 µm or less, for example, approximately 1, 7, 20, 35, 60 µm. The thickness can be measured using test methods commonly employed in the prior art. In another embodiment, the unit area content of the ink composition coated on the surface of the glass substrate is 1.0x105 to 3x10'2g / cm2, preferably 2.0x105 to 2.5x102g / cm2, for example, 2.0x105 to 1x104g / cm2, 7.5x103 to 2.5x102g / cm2, 4.0x103 to 1.5χ102g / cm2, from 2.0χ103 to 9x103g / cm2, for example, 1.5χ105g / cm2, 2.5χ102g / cm2, 1.5χ102g / cm2, 9x103g / cm2, 2.0x10'5g / cm2, 7.9x10'3g / cm2, 4.8x10'5g / cm2, 9.6x105g / cm2, 9.5x10'3g / cm2, 2.4x10'2g / cm2, 1.4x10'2g / cm2, 5.7x103g / cm2, 4.8x103g / cm2, 2.8x103g / cm2, 3.3x103g / cm2, 8.4x103g / cm2. In step 2), the heating temperature must be sufficient to allow the ink composition coated on the glass substrate to modify the glass substrate with which it is in contact. In one embodiment, heating can be carried out at a temperature of approximately 550 to 750°C, preferably approximately 600 to 710°C, for example, approximately 600, 640, 650°C. In another embodiment, heating can be carried out for approximately 1 to 30 minutes, preferably approximately 3 to 15 minutes, for example, approximately 3, 10, 5 to 10 minutes. In one embodiment, the heating described in step 2) is a conventional heating process for manufacturing automotive glass, for example, after the mark is printed, the glass is placed in a hot bending oven to form a bending radian required for a glass. After heating, as shown in Figure 2, the surface and / or a certain depth of the glass substrate is modified. The lower limit of the modification depth is 5 nm or more, preferably 10 nm or more; the upper limit is 100 pm or less, preferably 50 pm or less, and most preferably 10 pm or less, for example, approximately 10 nm, 100 nm, 1 pm, 10 pm, 15 pm. The modification depth can be measured using conventional methods in the prior art, for example, SEM. In one mode, the modified glass substrate has a slightly higher reflectivity than the unmodified portion, i.e., the uncoated portion of an ink composition. However, the The transmissivity of the modified portion of the glass substrate is close to that of the portion without the ink composition coating, i.e., the unmodified portion. In one modality, the modified portion of the glass substrate is substantially transparent to the naked eye, meaning the mark is invisible to the naked eye, particularly in transmission. The portion of the glass substrate modified by an ink composition has a clear boundary and can be clearly distinguished from the unmodified portion, so that it can be easily read by a reading device. In one embodiment, as shown in Figure 2, after heating in step 2), a residue of the burned ink composition, for example, a gray ink residue, remains on the surface of the glass substrate. Therefore, after step 2), a step 3), i.e., removal of the residue generated by heating the surface of the glass substrate in step 2), is optionally included. The removal of the residue can be carried out using a conventional prior art method, for example, sweeping, water jetting, or brushing. The glass substrate can optionally be dried after the residue is removed to eliminate any moisture or solvent introduced onto the surface of the glass substrate during the residue removal step. The drying can be carried out using a conventional prior art method and performed at a conventional drying temperature.Drying can be carried out at a temperature of approximately 60°C or less, approximately 50°C or less, approximately 45°C or less, approximately 40°C or less, approximately 35°C or less, approximately 20°C or less, or at any other suitable temperature. Drying can be carried out, for example, for approximately 1 minute, 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 24 hours, or any other suitable time. Ink composition In the process for preparing a branded glass product according to the present invention, the specific type of ink used or its combination with the preparation process of the present invention is useful in achieving the branded glass product of the present invention. The ink composition of the present invention can change the composition of the glass substrate and / or increase the surface roughness of the glass substrate through ion exchange, doping, etching, penetration, or precipitation. For example, ion exchange can occur between the components of the ink composition and the components of the glass substrate. The components of the ink composition can enter the glass substrate through doping, etching, or penetration. The ink composition can interact with the glass substrate physically or chemically, causing it to precipitate onto the glass substrate. In one embodiment, according to the common understanding in the prior art, the ink composition of the present invention is not resistant to high temperatures. “High temperature” herein refers to the temperature commonly used in glass processing, such as bending or flexing, for example, approximately 500 to 800°C or 550 to 750°C. “Not resistant to high temperatures” means that the ink composition, under such temperatures, would not retain its substantially original color when coated or may form ash. The ink composition of the present invention shall be selected so that the mark can dry quickly and thus the clarity and integrity of the mark can be maintained during subsequent processing, for example, cutting or grinding, of the glass substrate. The ink composition of the present invention shall also be selected so that the clarity and integrity of the mark can be maintained during subsequent processing, for example, cleaning process, of the glass substrate. The ink composition of the present invention shall be selected so that it can be used to modify the surface of the glass substrate under heating conditions. In one embodiment, the ink composition of the present invention is selected so that the surface of the glass substrate can be modified to produce an "invisible mark." In another embodiment, a coloring component may also be added to the ink composition so that the surface of the substrate can be modified during the heating process to produce a visible mark. In one embodiment, the ink composition comprises a halogen-containing and / or phosphate-based compound. Surprisingly, the addition of the halogen-containing and / or phosphate-based compound is useful for modifying the glass components via the ink composition. Specifically, the halogen-containing compound is useful for extracting alkali ions, such as sodium and potassium ions, from the glass substrate. This extraction, for example, leads to recombination of the densified components of the glass substrate, thereby modifying the optical index of the glass substrate. For instance, the reflectivity of the modified portion of the substrate is slightly higher than that of the unmodified portion. Since the depth of the modified portion of the glass substrate is only approximately 5 nm at 100 pm, there is no significant effect on transmission. The extraction of alkali ions can also densify the glass substrate, thereby improving the corrosion resistance of the substrate with the marked portion and enhancing the weather resistance of the marking.Halogen-based compounds can be organic compounds containing a halogen functional group, for example, those containing chlorine, such as bisphenol A-epichlorohydrin copolymers, those with CAS number 25068-38-6. In one embodiment, the ink composition is Markem-lmaje 5144M, which contains bisphenol A-epichlorohydrin polymer (CAS number 25068-38-6). The step-average molecular weight of the bisphenol A-epichlorohydrin polymer is approximately 40,000. In one embodiment, on the basis of the total weight of the ink composition, the lower limit of the content of the halogen-containing compound is 0.5% by weight or more, preferably 1% by weight or more; the upper limit of the content of the halogen-containing compound is 10% by weight or less, preferably 5% by weight or less; and / or the lower limit of the content of the element phosphorus in the phosphorus-based compound is 0.05% or more, preferably 0.1% or more, more preferably 0.15% by weight or more; the upper limit of the content of the element phosphorus in the phosphate-based compound is 4% by weight or less, preferably 3% by weight or less, more preferably 2.5% by weight or less. When phosphorus-containing glass is used as a glass substrate, an ink containing a phosphate-based compound may diffuse more readily into the glass substrate and thus modify it. The phosphate-based compound includes both inorganic and organic phosphate compounds. For example, the phosphate-based compound may be a phosphorus-containing initiator (phosphine) such as phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, a compound with CAS number 1187441-10-6, or a combination thereof. In one embodiment, the ink composition is Tiger Series 140 / 1, which contains phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide and a compound with CAS number 1187441-10-6. In one embodiment, based on the total weight of the ink composition, the phosphate content is approximately 2.5 to 11% by weight, preferably approximately 2.5 to 10% by weight. In another embodiment, based on the total weight of the ink composition, the phosphorus content in the phosphate-based compound is approximately 0.05 to 4% by weight, preferably approximately 0.1 to 3% by weight, more preferably 0.15 to 2.5% by weight, for example, 0.19 to 0.74% by weight, 0.44 to 0.89% by weight, or 0.89 to 2.22% by weight. In one embodiment, the ink composition of the present invention may optionally include one or more of the following: an acrylic acid / acrylate-based compound / polymer, a photoinitiator, an amine-modified monomer / oligomer, a thiol-modified compound / monomer, and an organic pigment. The acrylic acid / acrylate polymer compound is a compound having an acrylic acid / acrylate group and a polymer having an acrylic acid / acrylate group.Whereas, acrylic acid / acrylate includes, but is not limited to, monoacrylic acid / acrylate monomer, difunctional acrylic acid / acrylate monomer, trifunctional acrylic acid / acrylate monomer, tetrafunctional or higher acrylic acid / acrylate monomer and the polymer thereof, for example, (methyl) methacrylate, ethyl (methyl) acrylate, n-butyl (methyl) acrylate, isobutyl (methyl) acrylate, isooctyl acrylate, (methyl) acrylic acid, glycidyl (methyl) acrylate, hydroxyethyl (methyl) acrylate, cycloaliphatic acrylate monomer, tetrahydrofurfuryl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, hydroxypropyl (methyl) acrylate, isobornyl acrylate, tri(propylene glycol) diacrylate, trimethylolpropane triacrylate and those having CAS numbers 86273-46-3, 63225-53-6, 13048-33-4, 66492-51-1, 111497-86-0, 94624-09-6, 84170-74-1, 1187441-10-6, 28961-43-5 or combinations thereof.The polymer comprising an acrylic acid / acrylate group includes, but is not limited to, polystyrene-acrylate, polystyrene-acrylic acid. The ink composition can be selected, for example, as a heat-curing type or a photo-curing type. When a photo-curing type ink is used, a photoinitiator is usually incorporated. The photoinitiator is a commonly used photoinitiator in a UV-curing type ink composition, which includes, but is not limited to, benzoin ethers, azos, alkylphenones, acyl phosphorus oxides, thioxantrones, iodonium salts, eumene or ferrocene hexafluorophosphate, or combinations thereof; for example, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, a compound having CAS number 1187441-10-6, or combinations thereof. The amine-modified monomer / oligomer includes, but is not limited to, N-vinylcaprolactam, a compound having CAS number 11149786-0, ethoxylated cocoamine, or combinations thereof.The thiol-modified compound / monomer can be, for example, a thiol-modified compound that has oxidation resistance or that inhibits a crosslinking reaction under UV irradiation. In one embodiment, the ink composition does not include pigment, particularly organic pigment. Organic pigment includes, but is not limited to, azo pigment, phthalocyanine pigment, quinacridone pigment, arylmethane pigment, and the like, which give the ink different colors. For example, organic pigments exhibit blue, yellow, magenta, and cyan. The ink composition may also optionally include a solvent. The solvent includes, but is not limited to, water, ketones, and alcohols, for example, methyl ethyl ketone, isopropyl alcohol, ethanol, and the like. The ink composition may also optionally comprise one or more of the following additives, which include, but are not limited to, surfactant, wetting agent, thinner, antifoaming agent, adhesive promoter, rheology modifier, leveling additive, stabilizer, dispersant, inhibitor and the like, for example, ethoxylated cocoamine, glycidyl 12-14 alkyl ether. In one embodiment, the ink composition comprises a halogen-containing compound, an amine-modified monomer / oligomer, a solvent, and a diluent. In another embodiment, the ink composition comprises an acrylic acid / acrylate-based compound / polymer, an initiator containing phosphine, and an amine-modified monomer / oligomer. In one embodiment, the content of organic components in the ink composition of the present invention is approximately 70% or more, preferably approximately 80% or more, and most preferably approximately 90% or more. For the preparation of glass products with the “invisible mark” or “mark invisible to the naked eye”, it is preferable to avoid the use of inorganic compounds so that the (organic) residue of the ink composition located on the surface of the glass substrate could be completely cleared after the heating process. In a preferred embodiment, the ink composition comprises only a small amount of inorganic components. In one embodiment, the ink composition does not comprise silicon dioxide. In another embodiment, the ink composition does not comprise glass frit. In yet another embodiment, the ink composition does not comprise inorganic pigment. The exemplary ink composition is, for example, Markem-lmaje 5144M, Tiger TIGITAL, for example, Series 140 / 1 (blue, yellow, or magenta) (where the lower limit of the phosphorus element content is 0.19% or more, and the upper limit is 0.74% or less), Marabú Ultra Jet DLE-A cyan 459, yellow 428, or magenta 438 (where the lower limit of the phosphorus element content is 0.89% or more, and the upper limit is 2.22% or less), Nazdarv 710 UV / LED inkjet ink (yellow and cyan) (where the lower limit of the phosphorus element content is 0.44% or more, and the upper limit is 0.89% by weight or less). The aforementioned ink color, for example, blue, yellow, and the like, is the ink color of the ink composition before high-temperature treatment. To prepare glass products with visible markings, colorants are added to the ink composition. These colorants include, but are not limited to, cobalt ion-containing compounds and gold-containing nanoparticles, resulting in inks that are gray, yellow, or red, making the markings visible. The use of an ink composition is also provided in the process for preparing a glass product bearing the mark of the present invention or for preparing a glass product with the i / ui uoi a mark of the present invention. In the present invention, the combination of a specific ink composition with the preparation process is beneficial in obtaining a branded glass product that has the desired beneficial effects of the present invention. Branded glass product A branded glass product comprising a glass substrate is provided. The "glass" of the present invention is not particularly limited with respect to its field of application; for example, it may be architectural glass, automotive glass, and the like. For automotive glass, it may be front / rear windshield glass, door glass, or a skylight. The glass of the present invention is not particularly limited with respect to the preparation process; for example, it may be float glass, flat glass, tempered glass, laminated glass, and the like. The composition of the glass of the present invention is also not particularly limited; for example, it may be silicate glass, colored glass, borosilicate glass, and the like. In this context, the "glass substrate" has two opposing surfaces; an ink composition can be coated onto either surface of the glass substrate according to current requirements. In the case of laminated glass, the glass product usually contains more than two glass substrates; an ink composition can be coated onto any of these surfaces according to current requirements. The size of the mark on the glass product of the present invention is not particularly limited; for example, it can have a general size and resolution that the mark might usually have. For example, it has a size and resolution typical of an identification code and can thus be identified by a reading device. Any mark size can be established according to current requirements. In one embodiment, at least a portion of the mark is affixed beneath the surface of the glass substrate and extends along the thickness of the glass substrate from the surface to the interior. Depending on the location of the coated ink composition on the surface of the glass substrate, at least a portion of the glass substrate surface may be coated with the ink composition. In one embodiment, the lower limit of the mark depth extending along the surface of the glass substrate to the interior is 5 nm or more, preferably 10 nm or more; the upper limit of the depth is 100 pm or less, preferably 50 pm or less, and most preferably 10 pm or less. Therefore, on the surface of the resulting glass product, there is no deposition of the ink composition, and thus no substantial adhesion or scratching of the mark caused by the presence of the ink composition on the surface of the glass substrate. In one embodiment, the mark contains particles. The lower limit of the particle size is 150 nm or larger, preferably 200 nm or larger; the upper limit of the particle size is 600 nm or smaller, preferably 350 nm or smaller, most preferably 300 nm or smaller. When the particles are spherical, the size may be referred to as the particle diameter. In one embodiment, the particles are irregularly shaped. The size could be understood as the equivalent spherical diameter of the particles, i.e., the diameter of a sphere having the same volume as the particle. The particle size makes it more sensitive to light sources with shorter wavelengths, for example, UV / blue light. In UV / blue light, the particles have a certain degree of diffraction capability, and thus the mark is legible by reflection.Blue light or UV light diffracted by the mark would be absorbed by the glass as it passes through, with low transmission and difficulty penetrating the glass. In one form, the particles are crystals. In one modality, the crystal density is approximately 60 to 100 per 10 pm2, preferably approximately 70 to 90 per 10 pm2. The crystal density is obtained, for example, by microscopic observation, such as using an optical microscope or an electron microscope, for example, a scanning electron microscope. In another modality, the roughness of the surface of the glass substrate in the place with the mark is greater than without the mark. The optical properties of the portion bearing the brand of the glass product according to the invention can be characterized using the following method. In one embodiment, in the glass product bearing the mark of the present invention, the mark is invisible. The mark is invisible to the naked eye under transmitted light. Preferably, the mark is invisible to the naked eye in daylight, natural light, visible light, ambient light, cool white LED light, or blue light, etc., under transmitted light. Furthermore, the mark is not identifiable under transmitted UV light. In another embodiment, the mark is invisible to the naked eye under ambient indoor and outdoor light sources. For example, when the glass product is a vehicle window, passengers might not see the mark while sitting in the car or standing outside the car in everyday life. In one embodiment, the mark on the glass product of the present invention is invisible to the naked eye in daylight, natural light, visible light, or reflected ambient light. In another embodiment, the mark is invisible to the naked eye in reflected ambient light from an indoor or outdoor source. In yet another modality, when a marked glass product is tested using a D65 light source, the color difference value ΔΕτ of the marked portion compared to the unmarked portion (control glass) in transmission is approximately 0.5 or less, for example, approximately 0.4, 0.2 or close to 0. In one modality, when a glass product with the mark is tested using a D65 light source, the color difference value ΔΕη of the marked portion compared to the unmarked portion (control glass) in reflection is approximately 3 or less, e.g., approximately 0.85 to 2, e.g., 0.9, 1.5. In another modality, the value of the color difference ΔΕτ of the glass product with the mark in transmission is less than the value of the color difference ΔΕη in reflection. In one embodiment, the mark on the glass product of the present invention is legible. In another embodiment, the mark is legible under a light source whose spectral peak is located in the blue and / or UV light range. In yet another embodiment, the mark is preferably legible under a light source whose spectral peak is located between 100 and 480 nm in reflected light, for example, neon light, cool white LED light, blue light, UV light, or collimated light. In another modality, in a trademark image captured by an imaging device, for example, a camera or a microscope, under the light source whose spectral peak is located between 100 and 480 nm, preferably in the blue light and / or UV light portion, for example, Neon light, cool white LED light, blue light, UV light or collimated light, the trademark is clear and integral and the mark edge is clear, which is significantly different from the portion without the trademark.In one embodiment, the illuminance of the light source is 2000 lux or more, preferably 3000 lux or more, and most preferably 4000 lux or more; preferably, the light source is collimated. In a preferred embodiment, the mark could be read under dark-field conditions. Reading under dark-field conditions could improve the contrast of the mark and increase the color difference between the marked and unmarked portions, so that the mark could be easily read by a reading device. In one embodiment, the mark can also be affixed to the surface of the glass substrate. In one embodiment, in the glass product bearing the mark according to the present invention, the mark is an identification code, for example, such as that mentioned herein, for example, Data Matrix code, barcode, two-dimensional code and QR code. Examples The following Example describes the glass product bearing the mark of the present invention and the process of preparing it in detail with reference to the specific figures and modalities, but does not constitute a limitation to it. Testing methods The ΔΕτ and ΔΕη were measured using a Minolta color difference meter, where the light source was D65. The surface roughness of the glass substrate was measured using a Bruker Dektak Profilometer. Example 1 Materials Ink composition: Markem-lmaje (Markem) 5144M (ink not resistant to high temperature; where bisphenol A-epichlorohydrin polymer (CAS No. 25068-38-6) was contained in the ink composition with a content of approximately 2% of the total weight of the ink composition). Preparation process With reference to Figure 2, the preparation process includes the following steps 1) Cleaning the glass substrate to be treated, 2) using the ink from Example 1 to inkjet print a two-dimensional code pattern on the surface of the glass substrate using a Markem-lmaje 9450 inkjet printer and the thickness of the ink on the surface of the glass substrate was 7 pm, 3) Heating the glass substrate from step 2), with a heating temperature of 650°C and a heating time of 5 to 10 min, 4) Use of a damp cloth to clean the ash from the ink composition that existed on the surface of the glass substrate after heating. Result The glass substrate obtained in step 2) was cleaned with a damp cloth and a dry cloth. The ink mark remains clear and intact after cleaning. The glass substrate obtained in step 2) was cleaned with a glass washing machine commonly used for cleaning glass. The mark also remains clear and intact after cleaning. The mark on the glass product obtained with the mark was further observed and tested, and the characteristics are listed as follows: The mark contains particles, and the particle size is 200 to 300 nm. Furthermore, the particles are crystals. Furthermore, at least a portion of the mark is located below the surface of the glass substrate, and the depth of the mark, extending along the thickness direction of the glass substrate from the surface to the interior, ranges from 100 nm to 10 pm. In the glass product with the mark, the surface roughness of the area coated with an ink composition on the glass substrate is increased compared to that before coating. Furthermore, the brand is invisible to the naked eye in transmitted light sources such as daylight, natural light, and ambient light where vehicle glass and architectural glass are usually located, and is invisible to the naked eye in reflected light from those sources. However, under dark UV light and collimated light of 4000 lux, the mark can be read by a reading device. Images of the glass products at the marked positions are shown in Figures 3a and 3b, respectively. From the figures, it can be observed that the mark is clear and integral, which is easily distinguishable from the uncoated portion of glass with an ink composition. Therefore, under dark UV light or collimated light of 4000 lux, an industrial scanner (e.g., the Cognex identification scanning device) can be used to read the mark on the glass product of the present invention, and thus the information related to the two-dimensional code mark can be read. Furthermore, the mark on the glass product obtained using the ink composition of Example 1 can withstand a washing machine and thus has good wear resistance. Examples 2 and 3 Materials Ink composition: TigerTIGITAL® Series 140 / 1, wherein phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide and the compound with CAS Number 1187441-10-6 were contained, with a content of 2.5 to 10% by weight and 0.1 to 1% by weight, respectively, wherein the content of element phosphorus is 0.19 to 0.74% by weight. Preparation process 1) Clean the glass substrate to be treated using a glass washing machine, 2) Use an ink composition for single-pass printing through a piezoelectric, drop-on-demand inkjet printhead. The printing temperature was 40°C. The thickness of the ink composition coated on the glass surface was 7 µm (Example 2) and 35 µm (Example 3, correspondingly the maximum amount of ink composition coated on the glass substrate surface being 2.8 x 10³ g / cm²). The printed pattern was a two-dimensional code. 3) Heat the glass substrate from step 2), with a heating temperature of 640°C and a heating time of 3 min. Result The brand was observed and tested on the glass product obtained with the brand, and the characteristics are listed as follows: As shown in Figure 4, the mark contains particles and the particles are those fine white dots in large quantities shown in this Figure with a particle size of 200 to 300 nm and a particle density of 70 to 90 per 10 pm2. Furthermore, at least a portion of the mark is present below the surface of the glass substrate, and the depth of the mark extending along the thickness direction of the glass substrate from the surface of the glass substrate to the interior is 10 nm to 15 pm. Furthermore, in the glass product with the brand, the surface roughness of the position that is coated with an ink composition increased compared to that to be coated. As in Example 1, in the glass product with the mark obtained according to Example 2, the mark is invisible to the naked eye in transmitted light sources such as daylight, natural light, ambient light where vehicle glass and architectural glass are usually located, and the mark is also invisible to the naked eye in reflected light from those sources. Specifically, in the glass product of Example 2, the value of the color difference in transmission (ΔΕτ) of the glass substrate in the portion with the mark compared to the position without the mark is 0.4. In the glass product of Example 2, the value of the color difference in reflection (ΔΕπ) of the glass substrate in the portion with the mark compared to the position without the mark is 0.9. In the glass product of Example 3, the value of the color difference in transmission (ΔΕτ) of the glass substrate in the portion with the mark compared to the position without the mark is 0.2. In the glass product of Example 3, the value of the color difference in reflection (ΔEk) of the glass substrate in the portion with the mark compared to the position without the mark is 1.5. Figure 5 shows an optical microscope image of the glass product from Example 2 in a dark field of collimated light at 4000 lux. It can be clearly observed from the image that the edge of the mark is clear and the position where the ink composition was applied (i.e., the marked portion) can be clearly distinguished from the uncoated position. Thus, the image of the mark could be easily obtained by means of a reading device, and the information on the mark could then be read. Furthermore, the mark on the glass product with the mark obtained using the ink composition of Examples 2 and 3 can withstand a washing machine and thus has good wear resistance. Although the specific embodiments of the invention have been described above, it should be understood that they are for illustrative purposes only, and the scope of the invention is defined by the appended claims. Those skilled in the art may make various changes or modifications to the embodiments without departing from the spirit and scope of the invention, and such changes and modifications fall within the scope of the invention.

Claims

1. A process for preparing a branded glass product, characterized in that it comprises: 1) coating an ink composition onto a glass substrate surface, 2) heating the glass substrate obtained in step 1); wherein, in the resulting branded glass product, the brand contains particles having a size of 150 to 600 nm, preferably 150 to 350 nm, more preferably 200 to 300 nm.

2. The process for preparing a branded glass product according to claim 1, further characterized in that the particles are crystals.

3. The process for preparing a branded glass product according to claim 1 or 2, further characterized in that the ink composition comprises a halogen-containing compound and / or a phosphate-based compound.

4. The process for preparing a branded glass product according to claim 1 or 2, further characterized in that, on a weight basis of the total ink composition, the content of the halogen-containing compound is 0.5 to 10% by weight, preferably 1 to 5% by weight; and / or the phosphorus content in the phosphate-based compound is 0.05 to 4% by weight, preferably 0.15 to 2.5% by weight.

5. The process for preparing a branded glass product according to claim 1 or 2, further characterized in that the coating in step 1) is carried out by inkjet printing.

6. The process for preparing a branded glass product according to claim 1 or 2, further characterized in that the thickness of the ink composition coated on the surface of the glass substrate in step 1) is 1 to 100 µm, preferably 1 to 60 µm, more preferably 1 to 35 µm.

7. The process for preparing a glass product bearing a mark in accordance with claim 1 or 2, further characterized in that the heating in step 2) is carried out at a temperature of 550 to 750°C. 8.A branded glass product, characterized in that it comprises a glass substrate, wherein the brand contains particles having a size of 150 to 600 nm, preferably 150 to 350 nm, more preferably 200 to 300 nm.

9. The branded glass product according to claim 8, further characterized in that the particles are crystals.

10. The branded glass product according to claim 8, further characterized in that at least a portion of the brand is present beneath a surface of the glass substrate and extends along the thickness direction of the glass substrate from the surface of the glass substrate to the interior.

11. The branded glass product according to any one of claims 8 to 10, further characterized in that the brand is invisible to the naked eye in transmission. 12.The glass product bearing the mark of claim 11, further characterized in that the mark is invisible to the naked eye in daylight or reflected natural light.

13. The glass product bearing the mark of claim 11, further characterized in that the mark is legible under the following light source: the spectral peak of the light source is located in the blue and / or UV light range.

14. The glass product bearing the mark of claim 11, further characterized in that the mark is legible under neon light, cool white LED light, blue light, UV light, or collimated reflected light. 15.The glass product bearing a mark according to any of claims 8 to 10, further characterized in that the depth of the mark extending along the thickness direction of the glass substrate from the surface of the glass substrate to the interior is from 5 nm to 100 pm, preferably from 10 nm to 50 pm, more preferably from 10 nm to 10 pm.

16. The glass product bearing a mark according to any of claims 8 to 10, further characterized in that the mark is the identification code, for example, a Data Matrix code, a two-dimensional code, a QR code, or a barcode. 17.Use of an ink composition in a process for preparing a branded glass product as claimed in any of claims 1 to 7 or in the preparation of the branded glass product as claimed in any of claims 8 to 16, wherein the mark contains particles having a size of 150 to 600 nm, preferably 150 to 350 nm, more preferably 200 to 300 nm.

18. The use according to claim 17, wherein the particles are crystals.

19. The use according to claim 17, wherein the ink composition comprises a halogen-containing compound and / or a phosphate-based compound.

20. The use according to claim 17, wherein, on a total weight basis of the ink composition, the content of the halogen-containing compound is 0.5 to 10% by weight, preferably 1 to 5% by weight. and / or the phosphorus element content in the phosphate-based compound is 0.0.5 to 4% by weight, preferably 0.15 to 2.5% by weight.