Glass compositions for ink, glass with an ink layer, and ion-exchange strengthened glass with an ink layer

Abstract

This invention provides a glass composition for ink application, glass with an ink layer, and ion-exchange strengthened glass with an ink layer. The glass composition for ink application comprises: 15-30% SiO2, 25-50% Bi2O3, 10-20% Cr2O3, 5-15% CuO, 1-10% ZnO, 3-15% Al2O3, 1-10% Na2O, 0.5-10% K2O, 0.5-6% ZrO2, 0-8% MnO, 0.1-1% TiO2, and 0.1-1% Fe2O3. This invention also provides glass with an ink layer and ion-exchange strengthened glass with an ink layer. This invention enables chemical tempering of the printed areas of chemically strengthened glass, resulting in glass with high strength and minimal warping deformation caused by stress unevenness between the printed and non-printed areas, thus meeting the requirements of both ink printing and ion exchange strengthening.

Description

Technical Field

[0001] This invention relates to glass compositions for ink, glass with an ink layer, and ion-exchange strengthened glass with an ink layer, belonging to the field of laminated glass manufacturing technology. Background Technology

[0002] Current automotive chemically tempered laminated glass designs are limited in terms of appearance. The outer glass layer bears all printed decorative and functional layers, meaning that the black border, logos, and silver paste are all printed on the inner surface of the outer layer, while the inner glass layer remains unprinted. This approach results in all inner layer printed patterns being visible, negatively impacting the integration of laminated glass functions. For example, embedded copper foil, electrodes, and circuits cannot be effectively concealed, making it difficult to integrate functions such as dimming, display, and heating onto the chemically tempered laminated glass. Furthermore, the excessive decorative layers further weaken the strength of the outer glass layer, increasing the risk of cracking.

[0003] Moreover, since the printed masking layer forms a dense glassy layer after high-temperature sintering, which hinders ion exchange strengthening, this method of printing and sintering followed by chemical tempering will result in no strengthening effect on the printed area.

[0004] The existing technology of printing and sintering a decorative layer followed by chemical tempering involves printing and sintering a masking layer at high temperature, then chemically strengthening. However, this process suffers from two problems: firstly, the printed inks fade after chemical tempering, contaminating the ion exchange bath and causing it to fail; secondly, because there is no exchange in the printed area but exchange in the non-printed area, asymmetrical stress is generated on the two surfaces of the glass, causing deformation in the printed area during chemical tempering. Conversely, the method of chemically strengthening first, followed by printing high-temperature inks and sintering, results in the loss of compressive stress from chemical tempering due to the excessively high sintering temperature.

[0005] CN113924278A, CN117597232A, and other publications disclose some chemical tempering printing methods. These methods involve first printing porous ink, and the sintered ink layer will form a porous structure. After ion exchange, the printed area has a certain strengthening effect. Then, in order to solve the problem of light leakage at the pores, an additional organic masking layer needs to be coated on the printed area or the organic masking layer needs to be integrated on the surface of the intermediate film. The pores are filled during the lamination process. These methods place high demands on the porous ink material, and controlling the high-temperature sintering process to form a planar and uniform porous structure is very difficult to implement. In addition, the use of organic layer coating can easily lead to color difference with the original porous ink layer, and the durability is difficult to meet the requirements of automotive-grade decorative layers. The method of integrating the coating layer into the intermediate film can only be applied to the third side printing and cannot meet the printing requirements of the fourth side (the inner surface of the chemical tempered inner film).

[0006] Whether before or after chemical strengthening, it is impossible to print a high-temperature sintered shielding layer for automotive applications, resulting in all existing automotive chemically tempered glass being non-printed glass.

[0007] Therefore, how to solve the problem that the printed areas of chemically strengthened glass cannot achieve good chemical strengthening is one of the urgent problems to be solved in this field. Summary of the Invention

[0008] To address the aforementioned technical problems, the present invention aims to provide a glass composition for ink, wherein glass printing ink made from this glass composition allows K ions to pass through after sintering, thereby achieving ion exchange enhancement of the glass.

[0009] Another object of the present invention is to provide a glass printing ink made from the glass composition of the above-mentioned ink.

[0010] Another objective of this invention is to provide glass with an ink layer and a method for preparing the same. By pre-exchanging Na ions in the glass, followed by printing ink and then performing K ion exchange, ion exchange enhancement of the printed area can be achieved.

[0011] The present invention also aims to provide an ion-exchange strengthened glass with an ink layer prepared using the above-mentioned glass with an ink layer, and a method for preparing the same.

[0012] Another objective of this invention is to provide a laminated glass for automobiles that uses the aforementioned ion-exchange strengthened glass with an ink layer.

[0013] To achieve the above objectives, the present invention first provides a glass composition for ink, wherein, based on the mass of oxides, the glass composition for ink comprises the following components in the following mass percentages: 15%-30% SiO2, 25%-50% Bi2O3, 10%-20% Cr2O3, 5%-15% CuO, 1%-10% ZnO, 3%-15% Al2O3, 1%-10% Na2O, 0.5%-10% K2O, 0.5%-6% ZrO2, 0-8% MnO, 0.1%-1% TiO2, and 0.1%-1% Fe2O3.

[0014] The glass composition for ink provided by the present invention can be made into glass powder using existing glass powder preparation methods, and then used as raw material to make printing ink. After printing and sintering, a glass sintered body will be formed, which is capable of ion exchange.

[0015] According to a specific embodiment of the present invention, preferably, the glass composition for ink comprises the following components in weight percentages based on the mass of oxides: 20%-25% SiO2, 30%-40% Bi2O3, 15%-20% Cr2O3, 7%-11% CuO, 3%-10% ZnO, 5%-10% Al2O3, 3%-8% Na2O, 2%-6% K2O, 0.5%-3% ZrO2, 0-5% MnO, 0.1%-1% TiO2, and 0.1%-1% Fe2O3.

[0016] Compared with ordinary automotive glass inks, the glass composition for inks provided by this invention is a high-temperature sintering ink composition, which can bring the following technical effects: 1. The content of SiO2 and Al2O3 is significantly increased, which can form a [SiO4] and [AlO4] network structure that is conducive to ion exchange as much as possible, while improving the matching between the glass performance of the ink layer and the glass performance of the aluminosilicate substrate; 2. The content of Na2O and K2O is appropriately increased, which can increase the alkali metal oxide content of the ink body without affecting the glass structure and sintering performance of the ink layer, increase the diffusion concentration gradient effect, and improve the ion exchange efficiency.

[0017] The present invention further provides a glass with an ink layer, wherein the glass with an ink layer includes a glass substrate and an ink layer, the ink layer being formed on a portion of the surface of the glass substrate by glass printing ink of the aforementioned ink glass composition;

[0018] A sodium ion enrichment layer is formed on the surface of the glass substrate;

[0019] The sodium ion content in the sodium ion enrichment layer is ≥15wt%, preferably 15wt%-25wt%, based on the mass of Na2O.

[0020] The chemical tempering process of aluminosilicate glass is an ion exchange process based on the concentration diffusion effect. The high concentration of K ions in the salt bath used in the ion exchange creates stress after exchanging Na ions in the glass. The glass composition contains a certain amount of Na2O and K2O, and the proportion of Na2O must be significantly higher than that of K2O (generally, in conventional high-alumina glass composition, the Na2O content is not less than 1.5 times the K2O content) to form a sufficient Na-K concentration difference relative to the K salt bath, providing the necessary diffusion motive for successful exchange.

[0021] This invention increases the sodium ion concentration on the glass surface by forming a sodium ion enrichment layer below the glass surface. The sodium ion concentration in the enrichment layer is higher than that in the ink layer, thus creating a sodium ion concentration difference between the glass surface and the ink layer. Furthermore, the surface of the glass with the ink layer is free from compressive stress.

[0022] The glass powder raw materials for inks are generally low-melting-point bismuthate glass systems with a bismuth oxide content of at least 25%. The bismuth-oxygen bond-based glass structure imposes strict limitations on alkali metal raw materials; generally, the Na₂O content does not exceed 5%, the K₂O content does not exceed 2%, and the total alkali metal oxide content is less than one-third that of aluminosilicate glass. Further increasing the percentage of alkali metal oxides significantly affects the thermal stability and coefficient of thermal expansion of the bismuthate glass system, leading to mismatch with the glass matrix, glass cracking during high-temperature sintering, insufficient ink adhesion, and a series of other problems. Therefore, the surface of the ink layer cannot provide the required concentration gradient, making ion exchange difficult. Silica is not the main component of the ink layer's glass body, with a content generally between 10-25%. The alumina content of the ink layer's glass body is less than 2%. The limited number of [SiO₄] tetrahedra and [AlO₄] tetrahedra providing exchange channels in the ink layer's glass structure further restricts the diffusion and movement of Na and K ions within the ink layer.

[0023] During the sintering process of the ink layer in this invention, Na ions preferentially diffuse into the ink layer in large quantities (the Na ion content in the ink layer is lower than that in the glass substrate), which can fill the [SiO4] tetrahedra and [AlO4] tetrahedra in the glass body of the ink layer as much as possible, while increasing the Na ion content, thereby establishing the conditions for K ion exchange strengthening. When the glass with the ink layer provided by this invention is subjected to K ion exchange strengthening, K ions can be successfully exchanged to the ink layer, and diffusion conditions can be established on the surface of the ink layer and the glass substrate, so that K-Na exchange stress can also be generated on the glass surface, thereby allowing K ions to enter the interior of the glass substrate and achieve ion strengthening of the glass substrate area covered by the ink layer.

[0024] According to a specific embodiment of the present invention, preferably, the potassium ion content in the sodium ion enrichment layer is ≤5 wt% based on the mass of K2O. By controlling the potassium ion content of the sodium ion enrichment layer to a low level, it is beneficial to facilitate ion exchange between K ions entering the ink layer and the glass substrate during the K ion exchange strengthening process.

[0025] According to a specific embodiment of the present invention, preferably, the thickness of the ink layer is 5-30 μm, more preferably 5-15 μm. This ink layer thickness refers to the thickness of the ink layer after sintering. A lower ink layer thickness results in a smaller weakening effect on ion exchange, but also a lower ink masking ability, which may lead to defects such as light leakage and color difference; a thicker ink layer results in a more significant obstruction to ion exchange. Controlling the ink layer thickness within the above-mentioned range can avoid a strong weakening effect on ion exchange while maintaining the ink layer's masking ability.

[0026] According to a specific embodiment of the present invention, preferably, the area ratio of the ink layer on the surface of the glass substrate is ≤25%.

[0027] According to a specific embodiment of the present invention, preferably, the glass substrate comprises the following components by mass percentage, based on the mass of oxides: 50%-70% SiO2, 4%-22% Al2O3, 8%-18% Na2O, 0-5% Li2O, 0-1% CaO, 1%-5% MgO, 3%-10% K2O, 0-0.08% Fe2O3, 0-2% ZrO2, and 0-5% B2O3. More preferably, the glass substrate comprises the following components in weight percentage: 55%-65% SiO2, 8%-15% Al2O3, 10%-15% Na2O, 0-2% Li2O, 0-0.1% CaO, 3%-5% MgO, 5%-9% K2O, 0-0.08% Fe2O3, 1-2% ZrO2, and 1-5% B2O3.

[0028] According to a specific embodiment of the present invention, preferably, the thickness of the glass with the ink layer is 0.7-1.2 mm.

[0029] According to a specific embodiment of the present invention, preferably, the flexural fracture strength of the printed area of ​​the glass with the ink layer is not less than 100 MPa, and the flexural strength of the printed area of ​​the glass with the ink layer is not less than 30% of the flexural strength of the non-printed area of ​​the glass with the ink layer. By controlling the flexural fracture strength value of the printed area and the ratio between the flexural fracture strength of the printed area and the flexural strength of the non-printed area, glass warping due to uneven stress on the upper and lower surfaces of the printed area can be prevented.

[0030] According to a specific embodiment of the present invention, the glass composition for ink of the present invention can be used to make glass printing ink, and then an ink layer is formed on a portion of the surface of the glass substrate; that is, the present invention can also provide a glass printing ink containing the above-mentioned glass composition for ink.

[0031] According to a specific embodiment of the present invention, preferably, in the above-mentioned glass printing ink, the composition of the ink comprises 60%-75% structural components and 25%-40% auxiliary components by mass percentage; the structural components are the above-mentioned glass composition for ink.

[0032] According to a specific embodiment of the present invention, preferably, in the above-mentioned glass printing ink, the auxiliary components, by mass percentage, comprise 80%-90% organic solvent, 0.5%-1.5% additives, and 8%-15% binder.

[0033] The glass printing ink provided by this invention can be made using conventional methods for preparing glass printing inks.

[0034] According to a specific embodiment of the present invention, preferably, the auxiliary components, by mass percentage, comprise 80%-90% organic solvent, 0.5%-1.5% additives, and 8%-15% binder. The auxiliary components used can be those commonly used in ink layers, which volatilize during sintering. Specifically, the organic solvent can be selected from one or more combinations of terpineol, turpentine, diethylene glycol butyl ether, diethylene glycol butyl ether acetate, and hydrogenated castor oil; the additives include leveling agents and dispersants. Specifically, the leveling agent can be selected from one or more combinations of polyacrylic acid resins BYK350, 352, and 354; the dispersant can be selected from one or more combinations of TEGO Dispers 652, DA302N, and DISPER BYK-115 / 160 / 161 / 162 / 164 / 165; and the binder can be selected from one or more combinations of resin and ethyl cellulose.

[0035] The present invention also provides a method for preparing the above-mentioned glass with an ink layer, comprising the following steps:

[0036] Na ion exchange is performed on the surface of the glass substrate to form a sodium ion enrichment layer on the surface of the glass substrate.

[0037] An ink containing a glass composition for ink is printed on the surface of a glass substrate on which a sodium ion enrichment layer has been formed, and the ink layer is formed by sintering to obtain the glass with the ink layer.

[0038] According to a specific embodiment of the present invention, preferably, in the above-described method for preparing glass with an ink layer, the Na ion exchange is carried out using a NaNO3 salt bath with a purity ≥95wt%. If the concentration of the NaNO3 salt bath is lower than 95%, it will lead to Na enrichment on the glass surface. + Insufficient Na content leads to the transfer of Na to the ink layer during ink sintering. + Reduce, lower the second exchange K+ The penetration of the ink layer results in excessive differences in stress and strength between the printed area and the non-printed area, affecting the effectiveness of preventing glass warping.

[0039] According to a specific embodiment of the present invention, preferably, in the above-mentioned method for preparing glass with ink layer, the temperature of Na ion exchange is 350℃-430℃ and the time is 30-180min.

[0040] According to a specific embodiment of the present invention, preferably, in the above-described method for preparing glass with an ink layer, the sintering temperature is 500℃-700℃. This sintering process can be completed by separate heating and cooling processes, or it can be completed simultaneously with the glass bending and forming.

[0041] According to a specific embodiment of the present invention, preferably, in the above-mentioned method for preparing glass with an ink layer, after the Na ion exchange, the change in flatness warpage of the glass substrate is ≤0.1%. The technical solution provided by the present invention can control the warpage change of the glass substrate and minimize the glass warpage deformation caused by uneven stress.

[0042] According to a specific embodiment of the present invention, preferably, in the above-mentioned method for preparing glass with an ink layer, the printing is carried out by screen printing and / or inkjet printing.

[0043] According to a specific embodiment of the present invention, in the above-mentioned method for preparing glass with an ink layer, the original glass sheet can be cut and ground before ion exchange to form the required shape, which can be carried out in accordance with conventional methods in the art.

[0044] The glass with an ink layer provided by this invention does not require secondary coating or printing. During the K-ion exchange process, the glass in the printed area can also exchange ions with the molten salt, forming stress, thereby improving the strength of the glass in the printed area. At the same time, it reduces the glass warping deformation caused by uneven stress in the non-printed and printed areas, thus achieving the goal of chemically tempered glass that can simultaneously meet the requirements of ink printing and ion exchange strengthening.

[0045] The present invention also provides an ion-exchange strengthened glass with an ink layer, wherein the ion-exchange strengthened glass with an ink layer is obtained by K-ion exchange strengthening of the aforementioned glass with an ink layer.

[0046] According to a specific embodiment of the present invention, preferably, the surface compressive stress of the non-printed area of ​​the ion-exchange strengthened glass with ink layer is 500-900 MPa.

[0047] According to a specific embodiment of the present invention, preferably, the stress layer depth of the non-printed area of ​​the ion-exchange strengthened glass with ink layer is 30-50 μm.

[0048] According to a specific embodiment of the present invention, preferably, the flexural strength of the non-printed area of ​​the ion-exchange strengthened glass with ink layer is 300-600 MPa.

[0049] According to a specific embodiment of the present invention, preferably, the flexural strength of the printed area of ​​the ion-exchange strengthened glass with ink layer is 100-200 MPa.

[0050] The present invention also provides a method for preparing the above-mentioned ion-exchange strengthened glass with an ink layer, comprising the following steps:

[0051] The glass with the ink layer is subjected to K-ion exchange strengthening to obtain the ion-exchange strengthened glass with the ink layer.

[0052] According to a specific embodiment of the present invention, preferably, in the above-mentioned method for preparing ion-exchange strengthened glass with ink layer, the K ion exchange strengthening is carried out using a KNO3 salt bath with a purity ≥95%wt.

[0053] According to a specific embodiment of the present invention, preferably, in the above-mentioned method for preparing ion-exchange strengthened glass with ink layer, the K ion exchange temperature is 380℃-450℃ and the time is 120-480min.

[0054] According to a specific embodiment of the present invention, preferably, in the above-mentioned method for preparing ion-exchange strengthened glass with ink layer, after K ion exchange, the warpage change of the glass is ≤0.3%.

[0055] The present invention also provides a laminated glass for automobiles, which includes an outer glass and an inner glass, wherein the inner glass is the aforementioned ion-exchange strengthened glass with an ink layer.

[0056] According to a specific embodiment of the present invention, preferably, the ink layer is the third or fourth side of the automotive laminated glass.

[0057] According to a specific embodiment of the present invention, preferably, the thickness of the outer glass is 2.6-5.0 mm.

[0058] According to a specific embodiment of the present invention, preferably, the outer glass is heat-strengthened glass or chemically strengthened glass.

[0059] According to a specific embodiment of the present invention, preferably, the automotive laminated glass further includes a film disposed between the outer glass and the inner glass. More preferably, the film is selected from one or more combinations of EVA film, PVB film, SGP film, and PU film.

[0060] The technical solution provided by this invention can achieve chemical tempering of the printed area of ​​chemically strengthened glass for automobiles, and the resulting glass has high strength. At the same time, the glass warping deformation caused by the stress unevenness between the non-printed and printed areas is small, which can meet the requirements of ink printing and ion exchange strengthening. Attached Figure Description

[0061] Figure 1 The results show the Na element distribution at the interface of the glass after Na+ exchange. Detailed Implementation

[0062] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0063] definition :

[0064] Printed area: The area on the glass surface covered by an ink layer.

[0065] Non-printed area: The area on the glass surface that is not covered by the ink layer.

[0066] Examples 1-3

[0067] Examples 1-3 each provide a laminated glass for automotive applications, which is prepared through the following steps:

[0068] 1. Produce the outer glass sheet according to existing processes, including cutting, grinding, printing, and heat-strengthening steps;

[0069] 2. Cut the inner glass sheet to the desired shape, and place the cut glass in a salt bath with NaNO3 purity ≥ 95wt% for Na+ exchange at 350-430℃ for 30-180 min; the test results of the interfacial Na element distribution of the glass after this Na+ exchange step are as follows. Figure 1 As shown;

[0070] 3. An ink layer is printed on the inner glass using an ink containing a glass composition for ink, as a masking layer. The inner glass is then subjected to high-temperature treatment at a temperature between the glass transition point and the softening point (500℃-700℃) followed by cooling and annealing. During the high-temperature treatment, the masking layer completes high-temperature sintering, while the inner glass is bent into a shape that matches the outer glass, thus obtaining an inner glass with an ink layer.

[0071] 4. The inner glass in step 3 is subjected to ion exchange strengthening. The inner glass with ink layer is placed in a salt bath with KNO3 purity ≥ 95wt% and exchanged at 380-450℃ for 120-480min.

[0072] 5. The outer glass sheet from step 1 and the inner glass sheet from step 4 are laminated and subjected to high pressure to obtain the automotive laminated glass.

[0073] The assembly process includes: cutting the intermediate layer according to the glass outline; stacking the outer glass, intermediate layer, and inner glass in sequence in a dust-free environment, aligning the overlapping edges, and passing them through two heating stages and two rolling stages (rolling temperature of 120℃ and rolling pressure of 0.3MPa) to remove the gas from the intermediate layer and to initially bond the intermediate layer to the glass.

[0074] The high-pressure process includes: placing the laminated glass in an autoclave, heating and pressurizing it, and maintaining the temperature and pressure for a period of time. The maximum temperature is 140℃, the maximum pressure is 1MPa, and the holding time is 30min. After the process is completed, the temperature and pressure are slowly reduced.

[0075] The glass composition (structural component of the ink) used in Examples 1-3 has the following composition: 5.86% Na₂O, 0.04% MgO, 4.16% Al₂O₃, 16.6% SiO₂, 3.43% K₂O, 0.08% CaO, 0.12% TiO₂, 19.12% Cr₂O₃, 5.41% MnO, 0.29% Fe₂O₃, 10.22% CuO, 1.42% ZnO, 4.35% ZrO₂, and 28.9% Bi₂O₃. Auxiliary components in the ink can be selected as needed; these auxiliary components volatilize during sintering and do not remain in the final ink layer.

[0076] In Examples 1-3, the outer glass sheet used has a thickness of 3.5 mm, specifically conventional soda-lime glass that has undergone physical tempering. The inner glass sheet has a thickness of 1.1 mm, a glass size of 120 × 50 mm, and an inner glass printing size (i.e., the size of the ink layer) of 120 × 10 mm. The composition of the inner glass sheet is: 59.8% SiO2, 14.3% Al2O3, 11.8% Na2O, 0.01% CaO, 4.85% MgO, 6.72% K2O, 0.02% Fe2O3, 1.5% ZrO2, and 1% B2O3.

[0077] Comparative Example 1

[0078] This comparative example provides a laminated glass for automotive applications, which is prepared through the following steps:

[0079] 1. Produce the outer glass sheet according to existing processes, including cutting, grinding, printing, and heat-strengthening steps;

[0080] 2. Cut the inner glass sheet into shape;

[0081] 3. Print an ink layer on the inner glass using ordinary ink as a masking layer, and then perform high-temperature treatment at a temperature between the glass transition point and the softening point (500℃-700℃) followed by cooling and annealing. During the high-temperature treatment, the masking layer completes high-temperature sintering, and at the same time, the inner glass is bent into a shape that matches the outer glass, thus obtaining an inner glass with an ink layer.

[0082] 4. The inner glass in step 3 is subjected to ion exchange strengthening. The inner glass with ink layer is placed in a salt bath with KNO3 purity ≥ 95wt% and exchanged at 380-450℃ for 120-480min.

[0083] 5. The outer glass from step 1 and the inner glass from step 4 are laminated and subjected to high pressure (using the same method as in Examples 1-3) to obtain the laminated glass.

[0084] The structural composition of the ordinary ink used in Comparative Example 1 is as follows: 20.2% SiO2, 39.2% Bi2O3, 18.9% Cr2O3, 8.87% CuO, 4.97% ZnO, 1.68% Al2O3, 3.17% Na2O, 0.14% K2O, 0.52% ZrO2, 2.31% TiO2, and 0.04% Fe2O3. The auxiliary components in the ink can be selected as needed. These auxiliary components will volatilize during the sintering process and will not remain in the final ink layer.

[0085] Comparative Example 2

[0086] This comparative example provides a laminated glass for automotive applications, which is prepared through the following steps:

[0087] 1. Produce the outer glass sheet according to existing processes, including cutting, grinding, printing, and heat-strengthening steps;

[0088] 2. Cut the inner glass into shape and place the cut glass in a salt bath with NaNO3 purity ≥ 95wt% for 30-180 min at 350-430℃.

[0089] 3. Using ordinary ink (the same as Comparative Example 1), an ink layer is printed on the inner glass as a masking layer. After high-temperature treatment at a certain temperature between the glass transition point and the softening point (500℃-700℃), the masking layer is cooled and annealed. During the high-temperature treatment, the masking layer completes high-temperature sintering. At the same time, the inner glass is bent into a shape that matches the outer glass, thus obtaining an inner glass with an ink layer.

[0090] 4. The inner glass in step 3 is subjected to ion exchange strengthening. The inner glass with ink layer is placed in a salt bath with KNO3 purity ≥ 95wt% and exchanged at 380-450℃ for 120-480min.

[0091] 5. The outer glass from step 1 and the inner glass from step 4 are laminated and subjected to high pressure (using the same method as in Examples 1-3) to obtain the laminated glass.

[0092] Comparative Example 3

[0093] This comparative example provides a laminated glass for automotive applications, which is prepared through the following steps:

[0094] 1. Produce the outer glass sheet according to existing processes, including cutting, grinding, printing, and heat-strengthening steps;

[0095] 2. Cut the inner glass sheet into shape;

[0096] 3. Using the inks of Examples 1-3, an ink layer is printed on the inner glass as a masking layer. After high-temperature treatment at a temperature between the glass transition point and the softening point (500℃-700℃), the masking layer is cooled and annealed. During the high-temperature treatment, the masking layer completes high-temperature sintering. At the same time, the inner glass is bent into a shape that matches the outer glass, thus obtaining an inner glass with an ink layer.

[0097] 4. The inner glass in step 3 is subjected to ion exchange strengthening. The inner glass with ink layer is placed in a salt bath with KNO3 purity ≥ 95wt% and exchanged at 380-450℃ for 120-480min.

[0098] 5. The outer glass from step 1 and the inner glass from step 4 are laminated and subjected to high pressure (using the same method as in Example 1) to obtain the laminated glass.

[0099] Blank comparison (inner film):

[0100] This comparative example provides a laminated glass for automotive applications, which is prepared through the following steps:

[0101] 1. Produce the outer glass sheet according to existing processes, including cutting, grinding, printing, and heat-strengthening steps;

[0102] 2. Cut the inner glass sheet into shape and place it in a salt bath with KNO3 purity ≥ 95wt% for 120-480 min at 380-450℃.

[0103] 3. The outer glass from step 1 and the inner glass from step 4 are laminated and subjected to high pressure (using the same method as in Example 1) to obtain the automotive laminated glass.

[0104] The specific process parameters for the embodiments and comparative examples are shown in Table 1:

[0105] Table 1

[0106]

[0107]

[0108] In Table 1, the ion exchange parameters are, in order, the type and concentration of the salt bath, the temperature of the ion exchange, and the time of the ion exchange.

[0109] The elemental composition of the ink layer (i.e., the masking layer) after high-temperature sintering in Step 3 of Examples 1-2 and Comparative Example 3 is shown in Table 2.

[0110] Table 2

[0111]

[0112] The performance of the glasses obtained in Examples 1-3, Comparative Examples 1-3, and the blank comparative example was tested. The specific test methods are as follows:

[0113] Bending strength :

[0114] The bending strength of the glass was tested using the conventional three-point bending method (GB / T 34171-2017 Test Method for Bending Properties of Thin and Ultra-thin Glass, Three-point Bending Method). Specifically, the inner glass was held with the printed side facing down and subjected to tension. The bending strength of the outer glass in step 1, the inner glass in step 4, and the laminated glass in step 5 were tested separately. The lower span was 100 mm, the loading speed was 5 mm / min, and the loading was continued until the glass broke. The formula σ = 3P × L / (2b × h) was used. 2 Calculate the three-point bending strength, where σ is the bending strength (MPa), P is the loaded breaking force (N), L is the lower span (mm), b is the specimen width (mm), and h is the specimen glass thickness (mm).

[0115] Flat plate warpage :

[0116] The flatness test method was used to test the warpage change of the inner glass in step 4 before and after the second ion exchange strengthening. Specifically, the sample was placed flat on the flatness table, and a sheet gauge was used to measure the maximum height of the glass edge from the platform. The result was then divided by the length of the glass diagonal as the warpage percentage.

[0117] The test results are shown in Tables 3 and 4.

[0118] Table 3

[0119]

[0120] Note: The bending strength of the inner glass in Examples 1-3 and Comparative Examples 1-3 represents the bending strength of the printed area. For clarity, they are listed in Table 3.

[0121] Table 4

[0122]

[0123] The test results in Tables 3 and 4 show that:

[0124] Although the inner glass produced using the ink material and preparation method of the present invention has a lower bending strength compared to unprinted blank glass, the overall bending strength of the laminated glass does not decrease significantly after being combined with the outer glass to form laminated glass. The chemical strengthening warping caused by the obstruction of ion exchange in the printing area is also within an acceptable range.

[0125] In contrast, the inner glass printing area in Examples 1-3 was not significantly strengthened, resulting in excessively low bending strength of the inner glass. This led to a significant decrease in the interlayer bending strength and a significant increase in chemically strengthened warpage, making it difficult to meet the manufacturing and performance requirements of automotive laminated glass.

[0126] Comparative Example 1 shows the existing technology process;

[0127] Comparative Example 2 uses a common shielding layer. Although it has undergone the first ion exchange, the ink layer is difficult to provide ion exchange channels. During the sintering process, Na+ on the glass surface is difficult to diffuse to the ink layer. During the second ion exchange process, K+ in the salt bath is also difficult to replace Na+ in the shielding layer and exchange to the glass surface.

[0128] Although Comparative Example 3 used an exchangeable shielding layer material, it was difficult to provide enough Na+ for exchange with K+ in the salt bath after sintering because it was not pre-exchanged. The ion diffusion concentration difference was insufficient, and K+ was also difficult to exchange from the ink layer to the glass surface to generate compressive stress and strength.

Claims

1. A type of glass with an ink layer, characterized in that, The glass with an ink layer includes a glass substrate and an ink layer, wherein the ink layer is formed on a portion of the surface of the glass substrate by an ink-glass composition. A sodium ion enrichment layer is formed on the surface of the glass substrate; The sodium ion content in the sodium ion enrichment layer is ≥15 wt% based on the mass of Na2O. Based on the mass of oxides, the glass composition for ink comprises the following components in the following mass percentages: 15%-30% SiO2, 25%-50% Bi2O3, 10%-20% Cr2O3, 5%-15% CuO, 1%-10% ZnO, 3%-15% Al2O3, 1%-10% Na2O, 0.5%-10% K2O, 0.5%-6% ZrO2, 0-8% MnO, 0.1%-1% TiO2, and 0.1%-1% Fe2O3.

2. The glass with an ink layer according to claim 1, characterized in that, The potassium ion content in the sodium ion enrichment layer is ≤5wt% based on the mass of K2O.

3. The glass with an ink layer according to claim 1, characterized in that, The thickness of the ink layer is 5-30 μm.

4. The glass with an ink layer according to claim 1, characterized in that, The glass substrate comprises the following components by mass percentage, based on the mass of oxides: 50%-70% SiO2, 4%-22% Al2O3, 8%-18% Na2O, 0-5% Li2O, 0-1% CaO, 1%-5% MgO, 3%-10% K2O, 0-0.08% Fe2O3, 0-2% ZrO2, 0-5% B2O3.

5. The glass with an ink layer according to claim 1, characterized in that, The thickness of the glass with the ink layer is 0.7-1.2 mm.

6. The glass with an ink layer according to claim 1, characterized in that, The flexural fracture strength of the printed area of ​​the glass with ink layer is not less than 100 MPa, and the flexural strength of the printed area of ​​the glass with ink layer is not less than 30% of the flexural strength of the non-printed area of ​​the glass with ink layer.

7. The glass with an ink layer according to claim 1, characterized in that, Based on the mass of oxides, the glass composition for ink comprises the following components in the following mass percentages: 20%-25% SiO2, 30%-40% Bi2O3, 15%-20% Cr2O3, 7%-11% CuO, 3%-10% ZnO, 5%-10% Al2O3, 3%-8% Na2O, 2%-6% K2O, 0.5%-3% ZrO2, 0-5% MnO, 0.1%-1% TiO2, and 0.1%-1% Fe2O3.

8. A method for preparing glass with an ink layer according to any one of claims 1-7, characterized in that, Includes the following steps: Na ion exchange is performed on the surface of the glass substrate to form a sodium ion enrichment layer on the surface of the glass substrate. An ink containing a glass composition for ink is printed on the surface of a glass substrate on which a sodium ion enrichment layer has been formed, and the ink layer is formed by sintering to obtain the glass with the ink layer.

9. The method for preparing glass with an ink layer according to claim 8, characterized in that, The Na ion exchange was carried out using a NaNO3 salt bath with a purity of ≥95wt%.

10. The method for preparing glass with an ink layer according to claim 8, characterized in that, After the Na ion exchange, the change in flatness warpage of the glass substrate is ≤0.1%.

11. An ion-exchange strengthened glass with an ink layer, characterized in that, The ion-exchange strengthened glass with an ink layer is obtained by K-ion exchange strengthening of the glass with an ink layer as described in any one of claims 1-7.

12. The ion-exchange strengthened glass with an ink layer according to claim 11, characterized in that, The surface compressive stress of the non-printed area of ​​the ion-exchange strengthened glass with ink layer is 500-900 MPa.

13. The ion-exchange strengthened glass with an ink layer according to claim 11, characterized in that, The stress layer depth in the non-printed area of ​​the ion-exchange strengthened glass with ink layer is 30-50 μm.

14. The ion-exchange strengthened glass with an ink layer according to claim 11, characterized in that, The flexural strength of the non-printed area of ​​the ion-exchange strengthened glass with ink layer is 300-600 MPa.

15. The ion-exchange strengthened glass with an ink layer according to claim 11, characterized in that, The flexural strength of the printed area of ​​the ion-exchange strengthened glass with ink layer is 100-200 MPa.

16. The method for preparing ion-exchange strengthened glass with an ink layer according to any one of claims 11-15, characterized in that, Includes the following steps: K-ion exchange strengthening is performed on the glass with ink layer as described in any one of claims 1-7 to obtain the ion exchange strengthened glass with ink layer.

17. The method for preparing ion-exchange strengthened glass with an ink layer according to claim 16, characterized in that, After the K ion exchange, the warpage change of the glass is ≤0.3%.

18. A laminated glass for automobiles, comprising an outer glass pane and an inner glass pane, characterized in that, The inner glass is the ion-exchange strengthened glass with an ink layer as described in any one of claims 11-15.

Images