High-temperature-resistant primer, application thereof and marking composition for honeycomb ceramics

Abstract

The invention provides a high-temperature-resistant primer and application thereof, and a marking composition for honeycomb ceramics, and relates to the technical field of honeycomb ceramic surface coatings, the high-temperature-resistant primer comprises the following components by mass: 35%-50% of colored particles, 3%-5% of an emulsifier, 5%-15% of epoxy resin, 5%-10% of a thickener, and 15%-20% of an organic solvent; wherein the colored particles include metal alkoxide particles; the primer is cured on the surface of the honeycomb ceramic to form a coating, and the identification information is marked on the coating, so that a clear and stable identification effect of the identification information can still be kept under a high-temperature condition, and the technical problem that the identification information is difficult to clearly display on a honeycomb ceramic primer layer in a high-temperature environment in the prior art is solved.

Description

Technical Field

[0001] The invention relates to the technical field of honeycomb ceramic surface coatings, in particular to a high temperature resistant primer and application thereof, and a marking composition for honeycomb ceramics. Background Art

[0002] With the accelerated development of trends such as intelligence, networking, electrification and sharing, the automotive industry has increasingly stringent requirements for product quality control and supply chain management. Especially in the field of exhaust emission control, the traceability of automotive parts has become an important means to ensure product quality and meet regulatory requirements. As the core component of the exhaust purification device, the honeycomb ceramic substrate plays a key role in exhaust treatment with its advantages such as high specific surface area, good thermal stability and mechanical strength. Due to its complex production process, large batch and individual differences, traditional identification methods are difficult to meet the traceability requirements of modern automobile manufacturing.

[0003] Honeycomb ceramic carriers need to face different conditions during use, such as the slurry of the coating manufacturer and the high temperature generated by the engine during use; the traceability information of honeycomb ceramics (usually QR code, barcode and product text batch number, etc.) needs to maintain traceability in different environments. Adding a special primer on the surface of the honeycomb ceramic carrier can not only serve as a protective layer to improve the durability of the ceramic carrier, but also achieve the traceability of the honeycomb ceramic carrier by embedding or printing identification information.

[0004] The primer should have good adhesion, high temperature resistance and corrosion resistance to ensure that the identification information can still be clearly displayed in a complex working environment. The primer coating process should be carefully designed and optimized to ensure that the coating is uniform and smooth, and that the identification information can be embedded or printed without damaging the ceramic carrier structure. At the same time, it should meet the requirements of other traceability technologies that cannot be directly applied on the carrier surface, such as laser printing technology or laser etching technology, which can form clear and lasting identification information on the primer layer, such as batch number, production date and manufacturer, thereby ensuring that the product source, production batch and quality status are clear at a glance.

[0005] At present, most honeycomb ceramic carrier manufacturers apply primer on the product surface only as a base to satisfy the storage of some honeycomb ceramic carrier information, and there is no clear requirement for its own performance. Prior art CN 108238817B discloses a primer that controls the composition and process parameters of the coating material, such as controlling the thermal expansion rate to 3.5×10 -6The following prevents cracks, enhances mechanical properties and heat shock resistance, but cannot guarantee the traceability of the primer after high temperature. At the same time, it only adapts to the requirements of laser printing and cannot meet the requirements of all coding methods. Prior art CN 104245859 B discloses a composition for a marking substrate and a marking substrate. The composition can take into account the needs of laser marking and ink marking while maintaining heat resistance and chemical resistance, but the heat resistance can only guarantee the requirement of 600℃3h, which cannot meet the requirements of primer traceability information under high temperature of the engine. Prior art US20210323882A1 discloses a honeycomb structure having a circumferential coating, and its surface has a printing area for printing, but it cannot guarantee the readability of the information on the primer under high temperature environment.

[0006] In view of this, the present invention is proposed. Summary of the invention

[0007] One of the purposes of the present invention is to provide a high temperature resistant primer, which forms a base with more pores at room temperature and then densifies at high temperature, which can significantly enhance the high temperature resistance of the ink of identification information (such as QR code) and ensure that the identification information can still maintain a clear and stable recognition effect under high temperature conditions.

[0008] The second object of the present invention is to provide an application of a high temperature resistant primer, which is conducive to achieving traceability of the honeycomb ceramic carrier by marking identification information, while ensuring the readability of the identification information in a high temperature environment.

[0009] The third object of the present invention is to provide a marking composition for honeycomb ceramics, which can maintain a clear and stable recognition effect under high temperature conditions, and can meet the urgent needs of industries, logistics and other fields for the reliability of identification information under high temperature environments.

[0010] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0011] In a first aspect, a high temperature resistant primer comprises the following components by mass percentage:

[0012] Coloring particles 35%-50%, emulsifier 3%-5%, epoxy resin 5%-15%, thickener 5%-10%, and organic solvent 15%-20%;

[0013] The colored particles include metal alkoxide particles.

[0014] Furthermore, the primer also includes low-temperature glass powder as a component;

[0015] The mass proportion of the low-temperature glass powder in the primer is 10%-15%.

[0016] Further, the metal alkoxide includes at least one of metal methoxide, metal ethoxide, metal isopropoxide and metal butoxide;

[0017] The metal includes at least one of aluminum and titanium.

[0018] Furthermore, the emulsifier includes at least one of a nonionic surfactant, an anionic surfactant and a cationic surfactant.

[0019] Furthermore, the viscosity of the epoxy resin is between 10000 mPa·s and 15000 mPa·s.

[0020] Furthermore, the thickener includes at least one of silica sol, cross-linked polyacrylic acid resin, acrylate, alkyl acrylate cross-linked copolymer and acrylate copolymer.

[0021] Furthermore, the organic solvent includes at least one of dimethyl carbonate and ethanol.

[0022] In a second aspect, a high temperature resistant primer as described in any one of the above items is used in a surface coating of a honeycomb ceramic.

[0023] In a third aspect, a marking composition for honeycomb ceramics comprises a coating formed by curing any of the above-mentioned high temperature resistant primers and identification information marked on the coating.

[0024] Furthermore, the identification information includes at least one of a QR code, a barcode and a text batch number.

[0025] Compared with the prior art, the present invention has at least the following beneficial effects:

[0026] The high temperature resistant primer provided by the present invention has various components and their proportions that cooperate with each other to form a base with more pores at room temperature, which is then densified at high temperature. The cured coating remains in a non-cracking state after being baked at 700°C for 5 hours, which can significantly enhance the high temperature resistance of the ink for identification information (such as a two-dimensional code), ensure that the identification information can still maintain a clear and stable recognition effect under high temperature conditions, and solve the technical problem that the identification information (such as a two-dimensional code) formed by the ink is easy to fade under high temperature conditions.

[0027] The application of the high temperature resistant primer provided by the present invention is conducive to achieving the traceability of the honeycomb ceramic carrier by marking identification information, and can also ensure the readability of the identification information in a high temperature environment.

[0028] The marking composition for honeycomb ceramics provided by the present invention can still maintain a clear and stable recognition effect under high temperature conditions, can meet the urgent needs of industries such as industry and logistics for the reliability of identification information under high temperature environments, and is conducive to improving the efficiency and accuracy of product traceability and information management. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0030] Figure 1 A schematic diagram of honeycomb ceramic identification information provided in one embodiment of the present invention.

[0031] Icon: 1-honeycomb ceramic body; 2-primer layer; 3-QR code; 4-product number. DETAILED DESCRIPTION

[0032] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] According to a first aspect of the present invention, there is provided a high temperature resistant primer, comprising the following components by mass percentage:

[0034] Coloring particles 35%-50%, emulsifier 3%-5%, epoxy resin 5%-15%, thickener 5%-10%, and organic solvent 15%-20%;

[0035] The colored particles include metal alkoxide particles.

[0036] It should be noted that the mass percentage of each component is based on the total mass of the primer.

[0037] In the present invention, typical but non-limiting mass percentages of colored particles are, for example, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%; typical but non-limiting mass percentages of emulsifiers are, for example, 3%, 4%, 5%; typical but non-limiting mass percentages of epoxy resins are, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%; typical but non-limiting mass percentages of thickeners are, for example, 5%, 6%, 7%, 8%, 9%, 10%; typical but non-limiting mass percentages of organic solvents are, for example, 15%, 16%, 17%, 18%, 19%, 20%.

[0038] The high temperature resistant primer provided by the present invention has various components and their proportions that cooperate with each other to form a base with more pores at room temperature, which is then densified at high temperature. The cured coating remains in a non-cracking state after being baked at 700°C for 5 hours, which can significantly enhance the high temperature resistance of the ink for identification information (such as a two-dimensional code), ensure that the identification information can still maintain a clear and stable recognition effect under high temperature conditions, and solve the technical problem that the identification information (such as a two-dimensional code) formed by the ink is easy to fade under high temperature conditions.

[0039] In a preferred embodiment, the components of the primer of the present invention further include low-temperature glass powder;

[0040] The mass proportion of low-temperature glass powder in the primer can be 10%-15%, for example, 10%, 11%, 12%, 13%, 14%, 15%, but not limited thereto.

[0041] In the present invention, the particle size of the low-temperature glass powder can be 1μm-3μm, for example, 1μm, 2μm, 3μm, but not limited to this; at the same time, the pH value of the low-temperature glass powder can be 6-7, and the density can be 2.7g / ml, but not limited to this; the Mohs hardness of the low-temperature glass powder can be 7.8, but not limited to this.

[0042] In a preferred embodiment, the metal alkoxide includes but is not limited to at least one of metal methoxide, metal ethoxide, metal isopropoxide and metal butoxide;

[0043] The metal includes but is not limited to at least one of aluminum and titanium.

[0044] In the present invention, metal alkoxides can be prepared from metal oxides and alcohol solvents; wherein the metal oxides include but are not limited to at least one of aluminum oxide and titanium oxide, and the alcohol solvent is selected from alcohol compounds that can form alkoxides with the metal oxides, for example, at least one of methanol, ethanol, isopropanol and butanol.

[0045] In a preferred embodiment, the emulsifier includes but is not limited to at least one of a nonionic surfactant, an anionic surfactant and a cationic surfactant, or can be a combination of a nonionic surfactant and other types of surfactants.

[0046] In a preferred embodiment, the epoxy resin has a viscosity of 10000 mPa·s-15000 mPa·s, and typical but non-limiting viscosities are, for example, 10000 mPa·s, 11000 mPa·s, 12000 mPa·s, 13000 mPa·s, 14000 mPa·s, and 15000 mPa·s.

[0047] In a preferred embodiment, the thickener includes but is not limited to at least one of silica sol, cross-linked polyacrylic resin, acrylate, alkyl acrylate cross-linked copolymer, and acrylate copolymer.

[0048] In the present invention, the thickener can be selected from silica sol with a viscosity of 30 mPa·s - 45 mPa·s, or cross-linked polyacrylic resin or acrylate or alkyl acrylate cross-linked copolymer or acrylate (ester) copolymer particles with 15 μm < D50 < 25 μm.

[0049] In the present invention, the organic solvent can be selected from dimethyl carbonate with a purity of 98% - 99.5% or other alcohol-based solvents.

[0050] A method for preparing a high-temperature resistant primer, comprising the following steps:

[0051] According to the component mass ratio, first add coloring particles and low-temperature glass powder to a small mixing device for dry mixing, and then sequentially add an organic solvent, a thickener, an epoxy resin, and an emulsifier for mixing to form a white milky fluid with a certain fluidity, thereby obtaining the high-temperature resistant primer.

[0052] Under the synergistic cooperation of each component and its mass ratio, before curing, the high-temperature resistant primer has a viscosity of 8000 cpi - 12000 cpi and a density of 2.6 g / cm at room temperature 3 ; after curing, the coefficient of thermal expansion (room temperature - 800 °C) is 5 - 8×10 -6 , the HRC hardness is 6 - 11, the flexural strength is 8 MPa - 10 MPa, and the heat-resistant temperature is 1000 °C - 1400 °C.

[0053] According to the second aspect of the present invention, there is provided an application of the high-temperature resistant primer described in any one of the above in a coating on the surface of honeycomb ceramics.

[0054] The application of the high-temperature resistant primer provided by the present invention is conducive to realizing the traceability of honeycomb ceramic carriers through marked identification information, and at the same time can ensure the readability of the identification information in a high-temperature environment.

[0055] According to the third aspect of the present invention, there is provided a marking composition for honeycomb ceramics, comprising a coating formed by curing the high-temperature resistant primer described in any one of the above and identification information marked on the coating.

[0056] The marking composition for honeycomb ceramics provided by the present invention can still maintain a clear and stable recognition effect under high-temperature conditions, can meet the urgent needs of industries, logistics and other fields for the reliability of identification information in a high-temperature environment, and is conducive to improving the efficiency and accuracy of product traceability and information management.

[0057] A method for preparing a marking composition for honeycomb ceramics comprises the following steps:

[0058] The high temperature resistant primer is coated on the surface of the honeycomb ceramic, and after the primer is cured, the identification information (ie, traceability information) is marked on the surface of the primer layer to obtain a marking composition for the honeycomb ceramic.

[0059] In the present invention, the high temperature resistant primer can be applied by spraying or scraping, and can be applied to any position of the honeycomb ceramic except the inlet and outlet ends. The primer is cured to form a thin sheet on the surface of the honeycomb ceramic skin; wherein, the curing conditions of the primer can be cured at room temperature for 18h-24h, or can be cured at 110℃-200℃ for 15min-30min.

[0060] In the present invention, ink may be applied to form the identification information, or the identification information may be marked by laser coding.

[0061] In a preferred embodiment, the identification information includes but is not limited to at least one of a QR code, a barcode and a text batch number.

[0062] Typical identification information of a honeycomb ceramic, see the schematic diagram Figure 1 , a two-dimensional code 3 and a product number 4 can be printed on the primer layer 2 of the honeycomb ceramic body 1 by inkjet printing or laser printing.

[0063] In summary, the marking composition for honeycomb ceramics of the present invention, the primer layer and the traceability information marked thereon are calcined at 700° C. for 5 hours and cycled 4 times, and the two-dimensional code level can still meet the definition of level 4 of the AIM-DPM-1-2006 / ISO 29158 standard.

[0064] The present invention is further described below by way of examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or directly purchased from the market.

[0065] Examples 1-8

[0066] Embodiment 1-8 provides a marking composition for honeycomb ceramics, which is prepared by the following method:

[0067] (1) Preparation of high temperature resistant primer:

[0068] Weigh each component according to the ratio recorded in Table 1;

[0069] First, the colored particles and low-temperature glass powder are mixed and stirred for 5 minutes to 15 minutes to form a first component;

[0070] Among them, the particle size of low-temperature glass powder is 2 μm, pH value is 6, density is 2.7 g / ml, and Mohs hardness is 7.8;

[0071] Afterwards, the epoxy resin, emulsifier, thickener and organic solvent are mixed and stirred for 5-10 minutes to form a second component;

[0072] Among them, the viscosity of epoxy resin is 12000mPa·s;

[0073] Afterwards, add the first component to the second component and mix for 15-30 minutes to form a white fluid, that is, a high temperature resistant primer is obtained;

[0074] (2) Primer curing:

[0075] The obtained high temperature resistant primer is transferred to the surface of the honeycomb ceramic by spraying and cured to form a primer coating;

[0076] The curing method in Examples 1-7 is curing at room temperature, and the curing method in Example 8 is curing at 150°C;

[0077] (3) Marking information:

[0078] A QR code and a product number are printed on the formed primer coating. The specific printing method is shown in Table 1, thereby forming a marking composition for honeycomb ceramics.

[0079] Comparative Examples 1-8

[0080] Comparative Examples 1-8 provide a marking composition for honeycomb ceramics, which differs from Example 1 in that the components and their proportions in the high temperature resistant primer are shown in Table 1;

[0081] Meanwhile, the curing method in Comparative Example 7 is to perform curing at 150°C;

[0082] The specific printing methods of the QR codes and product numbers in Comparative Examples 1-8 are shown in Table 1;

[0083] The rest is the same as in Example 1 to form a marking composition for honeycomb ceramics.

[0084] Table 1

[0085]

[0086] Test example

[0087] The performance test results of Examples 1-8 and Comparative Examples 1-8 are shown in Table 2 and Table 3, respectively.

[0088] Performance testing method:

[0089] Thermal expansion coefficient CTE test: Make the primer into small pieces, place them in a thermal expansion tester, and test their thermal expansion coefficient between 25℃-800℃;

[0090] Viscosity test: The test was conducted using the NDJ-5S rotational viscometer from Shanghai Pingxuan Scientific Instrument Co., Ltd., with the speed set at 4 rpm;

[0091] Curing time test: After the primer is applied to the outer surface of the honeycomb ceramic, it is tested every 30 minutes, and the surface is lightly polished with 600-grit sandpaper until there is no primer powder on the sandpaper, which means it is completely cured;

[0092] Hardness test: The primer is prepared into a sheet material, and the Vickers hardness measurement method in GB / T 16534-2009 is used to measure the HA and convert it into HRC;

[0093] Bending strength test: The primer is prepared into sheet material, cut into 25mm-0.5mm specimens, and then placed in TH-8100S servo computer universal material testing machine for testing;

[0094] Use equipment that complies with ISO29158 standard to identify and read QR codes.

[0095] Table 2

[0096]

[0097] Table 3

[0098]

[0099] It can be seen from the performance data recorded in Table 2 and Table 3 that in terms of curing time, the average curing time of Examples 1-8 is relatively short, concentrated between 18h and 24h, while the average curing time of Comparative Examples 1-8 is longer, which indicates that Examples 1-8 have more advantages in curing speed; in terms of viscosity, the viscosity values ​​of Examples 1-8 vary in a smaller range and are generally lower than the Comparative Examples, which indicates that the primer has better fluidity during processing and is easier to operate.

[0100] The thermal expansion coefficient, as one of the important indicators of material performance, has changed in Table 2 and Table 3. Overall, the thermal expansion coefficients of Examples 1-8 are relatively low, which is conducive to maintaining better stability of the material when the temperature changes.

[0101] Hardness and bending strength are key parameters for measuring the mechanical properties of materials. It can be seen from Tables 2 and 3 that the hardness values ​​in Examples 1-8 are relatively stable, while the bending strength fluctuates among different examples, but are more competitive than the comparative examples as a whole; Comparative Examples 1-8 show greater differences in hardness and bending strength, especially a larger range of hardness values, which indicates the diversity of mechanical properties of materials obtained from different comparative examples.

[0102] It can be seen from the changes in the QR code level and the QR code level after calcination at 700°C for 20 hours that although the comparative examples and the embodiments have good QR code recognition before calcination, after calcination at 700°C for 20 hours, the QR code recognition in the comparative examples 1-8 is severely deteriorated, while the QR code recognition in the embodiments 1-8 shows better high temperature stability.

[0103] It can be seen that Examples 1-8 show good comprehensive performance in terms of curing time, viscosity, thermal expansion coefficient, mechanical properties, and high-temperature stability of two-dimensional code recognition, and have significant advantages over the comparative examples.

[0104] In summary, the marking composition for honeycomb ceramics of the present invention can still maintain a clear and stable recognition effect under high temperature conditions. After being calcined at 700°C for more than 20 hours, or calcined at 700°C for 5 hours and cycled 4 times, the primer layer and the two-dimensional code marked thereon can still remain clear without obvious deformation and cracking; the two-dimensional code before and after calcination meets the definition of level 4 of the AIM-DPM-1-2006 / ISO29158 standard.

[0105] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high temperature resistant primer, characterized in that: It includes the following components by mass percentage: Coloring particles 35%-50%, emulsifier 3%-5%, epoxy resin 5%-15%, thickener 5%-10%, and organic solvent 15%-20%; The colored particles include metal alkoxide particles.

2. The high temperature resistant primer according to claim 1, characterized in that: The components of the primer also include low-temperature glass powder; The mass proportion of the low-temperature glass powder in the primer is 10%-15%.

3. The high temperature resistant primer according to claim 1 or 2, characterized in that: The metal alkoxide includes at least one of metal methoxide, metal ethoxide, metal isopropoxide and metal butoxide; The metal includes at least one of aluminum and titanium.

4. The high temperature resistant primer according to claim 1, characterized in that: The emulsifier includes at least one of a nonionic surfactant, an anionic surfactant and a cationic surfactant.

5. The high temperature resistant primer according to claim 1, characterized in that: The viscosity of the epoxy resin is between 10000 mPa·s and 15000 mPa·s.

6. The high temperature resistant primer according to claim 1, characterized in that: The thickener includes at least one of silica sol, cross-linked polyacrylic acid resin, acrylate, alkyl acrylate cross-linked copolymer and acrylate copolymer.

7. The high temperature resistant primer according to claim 1, characterized in that: The organic solvent includes at least one of dimethyl carbonate and ethanol.

8. Use of the high temperature resistant primer according to any one of claims 1 to 7 in a surface coating of honeycomb ceramics.

9. A marking composition for honeycomb ceramics, characterized in that: The invention comprises a coating formed by curing the high temperature resistant primer according to any one of claims 1 to 7 and identification information marked on the coating.

10. The marking composition for honeycomb ceramics according to claim 9, characterized in that: The identification information includes at least one of a QR code, a bar code and a text batch number.

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