A medium (organic carrier) with high initial adhesion strength, developed for use in the composition of glass enamels.

Abstract

The invention relates to a water-based acrylic-melamine-based medium (organic carrier) developed for use in the composition of coating compounds such as glass coating compounds, thick and thin film components, and glass enamels, and which has a high initial adhesion strength property during the transport of glass enamels.

Description

TARIFF A medium (organic carrier) with high initial adhesion strength, developed for use in the composition of glass enamels. Technical Area The invention relates to a water-based acrylic-melamine-based medium (organic carrier) developed for use in the composition of coating compounds such as glass coating compounds, thick and thin film components, and glass enamels, and which has a high initial adhesion strength property during the transport of glass enamels. State of the Art Glass enamels are used in many areas, including glass tableware, glass packaging, oven glass, automotive glass, and architectural glass (appliance glass (oven doors, refrigerator shelves, glass-ceramics), glasswares (glass packaging-bottles), glass tablewares (glass tableware-cups, plates), ceramics (ceramics, plates, mugs), pharmaceutical industry (light bulbs), technical glass (electronics, photovoltaics), automotive industry (windshields, rear windows, side windows, sunroofs, etc.), and architectural glass), exhibiting decorative or functional properties depending on their application. Glass enamels are essentially three-component systems: glass frit (flux), inorganic pigment (coloring agent), and medium (carrier). Glass frits are glassy structures obtained by combining various metal oxides / carbonates or nitrates in specific proportions, melting them, and then pouring this melt into water (quenching) to achieve an amorphous structure. The glass frits used in glass enamels are produced in three stages: weighing / blending the raw materials, melting and pouring into water, and grinding. Weighing accuracy and homogeneous mixing are important considerations. The melting of the frit can be carried out in batch or continuous processes. After the melting process, the glass melt is poured into water to prevent crystallization. Then, it is ground into powder form and incorporated into the glass enamel structure. Glass enamels essentially consist of a functional glass frit with a lower melting point than ceramic and enamel frits, pigments with low thermal expansion and high color fastness (according to the CIE (Commission Internationale de l'eclairage) standard) and opacity, and organic medium structures. Glass enamels, especially those in black and white, have a wide range of applications in the industry. Black and white pigments are of great importance in enamel applications due to their decorative and functional properties. Glass frits are produced by combining raw materials such as silica (S1O2), boron oxide (B2O3), soda (Na2COs), titanium dioxide (T1O2), and zirconium oxide (ZrO2) in specified proportions and mixing them homogeneously. The melting temperature, coefficient of thermal expansion, chemical resistance, and stability of the product depend on the glass frit. Silica used in the structure of glass frits increases chemical resistance and firing temperature, while decreasing the coefficient of thermal expansion. Boron oxide decreases the coefficient of thermal expansion and firing temperature and increases chemical resistance. Molybdenum and fluorine increase the coefficient of thermal expansion and decrease the firing temperature. Zinc oxide provides opacity, while titanium dioxide increases acid resistance, and zirconium oxide increases alkali resistance. One of the most important features of glass enamel applications is the ability to obtain an opaque black enamel band on the outer corners of automotive front, side, and rear windows at low temperatures, as mentioned in patent application number WO2017127788A1. These opaque black bands vary in thickness from 1.5 cm to 15 cm in the industry. While this variation depends on aesthetic considerations and design, its primary purpose is to prevent degradation due to ultraviolet radiation by blocking sunlight emissions. Furthermore, this opaque black enamel band covers the silver-containing bus bar system and cable connections of the rear window defrosting system at the rear of the vehicle, providing UV protection. Among inorganic pigments, the spinel structure with the formula AB2O4 is preferred in the industry due to its stable crystalline structure. According to studies, CuCr2O4 has a spinel crystalline structure and exists in the tetragonal phase. (Cu,Mn,Cr)3O4, which contains MnOx, contains cubic, tetragonal and / or both phases. And as the amount of MnOx increases, the concentration of the cubic phase structure in the structure becomes higher. Inorganic pigments constitute approximately 15-25% of the formulation. They are synthesized using various chemical methods. The most common method involves the formation of inorganic complex structures via solid-state reaction. These structures are obtained by calcining one or more metal oxides / carbonates / hydrates or nitrates according to a specific recipe at temperatures between 850°C and 1400°C. Subsequently, grinding is applied to achieve the appropriate particle size. Here, the raw materials, their particle sizes and ratios, the achievement of a homogeneous mixture, furnace conditions, and ultimately the particle size of the synthesized pigment are critical processes in determining the color. The organic carrier (medium) is another essential component for the formation of glass enamel. The organic carrier (medium) includes binders (resins), solvents, dispersion agents, surfactants, and fillers. It helps to bring the powdered pigment and frit to a paint-like consistency. It also ensures the dispersion of the pigment and frit. It provides a liquid medium for obtaining a homogeneous mixture. Furthermore, it enables the glass enamel to acquire the applicable viscosity and rheology. In the known technique, glass enamel, prepared by mixing 60% glass frit, 20% medium, and 20% pigment, is applied to the glass surface using an appropriate method, followed by a drying process. After drying (100-180°C), a firing process (560-700°C) takes place, and the organic carrier is removed from the environment at these temperatures (clean burn-off). During the firing process, the glass frit binds to the glass surface, and the pigment remains in the system as a colorant. The problem encountered in the known production process of glass enamel is that the applied glass is transferred within the facilities and the firing process is not carried out immediately. After application and subsequent drying, the glass is transported both during the manufacturing process and to domestic and international distributors. There, the glass undergoes cutting, grinding, and other processes. The glass, having reached its final form, can then be tempered or fired. All these processes are carried out after drying but before firing. Therefore, the enameled glass coming out of the drying process must have high initial adhesion strength during these processes. Otherwise, defects will occur on the surface during these processes. The paint will peel off the glass surface, and the glass surface will lose its functional and / or decorative properties. To the known state of the art, a patent application, US2014107260A1, describes a liquid medium or vehicle for coating compositions such as ceramic coating compositions, thick and thin film compositions, glazes, and glass enamels. This medium is low in volatile organic compounds (VOCs) and contains a low VOC solvent such as propylene carbonate, dimethyl carbonate, or combinations thereof. In the known technique, some practical problems arose for the first medium with high adhesion strength. Here, solvents, binders, and resins negatively affected the drying time and application viscosity of the resulting composition, while also causing problems such as failure to clean on the sieve. Accordingly, a medium composition used in the formation of glass enamel is needed that provides acceptable drying and application properties. Consequently, due to the aforementioned drawbacks and shortcomings, the need for innovation in the relevant technical field has arisen. Purpose of the Invention The present invention relates to a medium (organic carrier) with high initial adhesion strength, developed for use in the construction of glass enamels, which meets the aforementioned requirements, eliminates all disadvantages, and introduces some additional advantages. The aim of this invention is to develop a water-based acrylic-melamine-based medium (organic carrier) for use in the composition of coating compounds such as glass coating compounds, thick and thin film components, and glass enamels, which possesses high initial adhesion strength during the transport of glass enamels. The aim of the invention is to provide a medium that offers high initial adhesion strength compared to standard mediums. The aim of the invention is to enable the production of glass enamels that, thanks to the medium, prevent the formation of defects on the glass surfaces to which they are applied. The aim of the invention is to enable the production of glass enamels that, thanks to the medium, retain the functional and / or decorative properties of the glass surfaces to which they are applied. One aim of the invention is to enable glass surfaces coated with glass enamel to acquire physical and chemical resistance. One aim of the invention is to produce a medium that is water-cleanable, has good flow properties, favorable initial adhesion strength, excellent drying rate, and an applicable viscosity range. One aim of the invention is to enable the glass surface to which the medium is applied to to become resistant to environmental influences. Another aim of the invention is to obtain a coating composition that is chemically stable at high temperatures. This allows glassware to withstand high temperatures in dishwashers and microwave ovens. To fulfill the purposes described above, the invention is a medium (organic carrier) containing a mixture of cellulose ether, a surfactant, a dispersing agent, and one or more solvents, developed for use in the composition of coating compounds such as glass coating compounds, thick and thin film components, and glass enamels. Its characteristic feature is that it contains acrylic resin and melamine resin to enhance the initial adhesion strength of glass enamels during transport. To achieve the purposes of the invention, the medium contains acrylic resin-melamine resin in a 3:1 ratio. To achieve the purposes of the invention, the medium has a viscosity value of 1,000-10,000 cPs at 25 °C and 15 rpm. To achieve the purposes of the invention, the medium is produced by adding acrylic resin, melamine resin, cellulose ether, surfactant, and dispersing agent to the solvent mixture in the mixing vessel, in that order, and mixing them. To fulfill the purposes described above, the invention is a medium developed for use in the composition of coating compounds such as glass coating compounds, thick and thin film components, and glass enamels. Its properties include being water-cleanable, having good flow properties, favorable initial adhesion strength, excellent drying rate, and an applicable viscosity range. The structural and characteristic features and all the advantages of the invention will be more clearly understood through the detailed description given below, and therefore the evaluation should be made taking this detailed description into account. Figures that will help understand the invention. Figure 1: Graph showing the drying performance of GMW 001 and GMW 002 at 150 °C for 45 minutes. Figure 2: Graph showing the drying performance of GMW 001 and GMW 002 at 100 °C for 45 minutes. Explanation of References in Figures: GMW 001 GMW 002 Detailed Description of the Invention This detailed description of the medium (organic carrier) with high initial adhesion strength, developed for use in the construction of glass enamels, is provided solely for the purpose of better understanding the subject and does not impose any limiting effects. The invention relates to a water-based acrylic-melamine-based medium (organic carrier) developed for use in the composition of coating compounds such as glass coating compounds, thick and thin film components, and glass enamels, and which has a high initial adhesion strength property during the transport of glass enamels. The subject of the invention is the medium's formulation; Content Available Amount by Weight (%) Acrylic resin (binder-1) 10-30 Melamine resin (binder-2) 2-10 Cellulose ether 2-5 Dispersion agent 1-5 Surfactant 1-3 Solvent mixture 45-84 The binder used in this invention is a water-based OH-functional thermosetting acrylic resin. Acrylic resins are obtained by the polymerization of acrylic monomers using specific catalysts and initiators. The monomers used in acrylic resin production are non-functional monomers such as methyl methacrylate, acrylic acid, butyl acrylate, and styrene; and OH-functional monomers such as 2-EHA, HPA, HPMA, and 2-HEA. Acrylic resins called thermoplastics are produced with non-functional monomers, while acrylic resins produced with functional monomers are called "thermoset" acrylic resins. The most important factors affecting product quality in acrylic resin production are monomer ratios, dosing time, dosing rate, catalyst type and quantity, and temperature. Binding-2 consists of melamine resins. Melamine resin is a thermoset material synthesized by the polymerization of melamine and formaldehyde. Reactive melamine resins have been used to increase product stability, particularly for oven-drying systems at temperatures between 100-140 °C. The reaction between melamine and acrylic occurs at oven-drying temperature. The glass enamel was cured in drying ovens with a medium containing acrylic resin-melamine resin in a ratio of 75%:25% (3:1) and the initial adhesion strength was tested. The surface was provided with physical and chemical resistance. The acrylic-melamine coating cross-linking structure is given in Formula-1 (1). X o \ ıı CH3^—CO(CH2)3CH3 / o )—coch2ch2och \0 CH34— CO(CH2)3CH3 / O \ ıı )—COH / O \ ıı )— COCH2CH2OH / o CH3A—CO(CH2)3CH3 N CH3OCH2H he CH3(CH2)3OC o II HOC o CH2OCH2CH2OC o CH3(CH2)3OC o II HOCH2CH2OC ch3ch3 Formula-1 Formula-2 shows the crosslinking structure and functional groups of melamine (2). 10 Here, the condensation of alkoxyl groups with hydroxyl groups on melamine and the condensation of carboxyl groups on the polymer resin and the condensation of hydroxyl groups on different melamines are the two reactions that dominate the system. In their study, Bauer and Dickie investigated the curing chemistry and network formation of solvent-based and water-based acrylic copolymer resins with different melamine-formaldehyde crosslinkers. 15 The initial adhesion strength of the medium in question is increased by increasing the curing temperature and melamine concentration. nr2—H —CH2OH R = — CH2OCH3—ch2oc4h9—CH2-(melamine) Formula 2 The condensation reaction of alkoxyl groups with hydroxyl groups on melamine and the condensation reaction of hydroxyl groups on different melamines are given in formula-3 (2). Melamine-Polymer Reaction (1) ^.N—CH2-O—CH3 + R—OH ^N-CH2-OR + CH3 OH 0 0 \ II H . 11 (2) / .N-CH2-O-CH3 + RC-OH ^N-CH2-OC--R + CH3-OH (3) \ H+ \ / N-CH2-O-C4H9 + R-OH / N CH2-0 R+C4H9 OH (4) / .n-ch2-o-c4h9 + RC-OH —— ^N-CH2-OC--R + C4H9—OH (5) ^N—CH2-OH + R-OH ^N-CH2-OR + H2O \ θ h+ \ θ (6) ^.N—CH2OH + RC-OH —— ^N-CHz-OC--R + H2O Melamine-Melamine Reaction (7) \ \ H+ \ . ^n-ch2-oh + / ,n-ch2-oh ^,n-ch2-n^ + CH2OH + H2O \ \ OH+ \ (8) N ch2-oh + ^N-CH2-OH ^N-CH2-O-CH2-N^ + H2O \ \ h+ \ (9) ^N-CH2-OH + ^NH \|-CH2-N^ + H2o Formula 3 Melamine groups can include hexamethoxymethylamine and contain OH, NH, and OCH3 groups, as well as small amounts of N-CH2-N groups. Melamine functional groups are methoxymethyl, butoxymethyl, methylol, amine, and methylene bridge groups. Acrylic resin functional groups are alkoxy, amine, and methylol groups. The formation of acrylic-melamine bonds can be described as the condensation reaction of a polymer with an f functional group and a monomer with a g functional group. Cellulose ethers are produced as specialized cellulose ethers in various modifications such as MC (methyl cellulose), HPMC (hydroxypropyl methyl cellulose), HEMC (hydroxyethyl methyl cellulose), and HEC (hydroxyethyl cellulose), depending on the production process. They are chemical products formed after a chemical process called etherification, where cellulose hydroxyl groups are replaced with methyl and / or hydroxypropyl groups, resulting in the conversion of cellulose into water-soluble nonionic cellulose ether. Hydroxypropyl cellulose, used as a thickening agent in formulations, is also an additive with many typical properties such as water retention aid, binder, dispersion aid, lubricant, colloid, or stabilizer. The medium (organic carrier) described in this invention contains one or more glycol ethers and / or esters as solvents. A wide range of glycol ethers and esters may be used. These may include EPh glycol ether or TPM glycol ethers, EB glycol ether (2-butoxyethanol), Texanol (2,2,4-trimethyl-1,3-pentanediol-1-isobutyrate), Texanol ester alcohol (2,2,4-trimethyl-1,3-pentanediolmono(2-methylpropanoate)), glycol ether esters, propylene glycol, dipropylene glycol and combinations thereof. Alkylol ammonium salts and modified urea solutions of copolymers with an acidic group can be used as dispersion agents, while ethoxylated alcohol groups and urea solutions can be used as surfactants. The production method for a medium with high initial adhesion strength; • Acrylic resin, melamine resin, cellulose ether, surfactant, and dispersing agent are added sequentially to the solvent mixture in the mixing container to obtain the medium. The viscosity of the resulting medium was measured at 25 °C with a BROOKFIELD VISCOMETER, DV2T, at 15 rpm and ranged from 1,000 to 10,000 cPs. The preferred application method for the invention requires that the medium in question be water-washable, have good flow properties (rhology), favorable initial adhesion strength (ASTM D3363) and excellent drying rate, and a usable viscosity range. Within the scope of this invention, glass enamels were prepared to compare the performance of the medium in question. Accordingly, two frit recipes were created: zinc-based (Zn-based) and bismuth-based (Bi-based). CuCr2O4 pigment with Mn additive was used for black color, and rutile TiO2 was used for white color. Table T shows the zinc-based glass frit composition, and Table 2 shows the bismuth-based glass frit composition. A total of four different enamel systems were prepared with the medium in question (GMW 002). Their comparative performance was compared with the product used in the industry (GMW 001). The dry film thicknesses of the glass enamels prepared here range from 25-50 µm. Figure 1 shows the drying performance of GMW 001 and GMW 002 at 150 °C for 45 minutes, and Figure 2 shows the drying performance of GMW 001 and GMW 002 at 100 °C for 45 minutes. Table 1: Zinc-based glass frit composition Component Mol (%) SiO2 30-51 Na2O 11-20 B2Os 10-20 ZnO 20-25 F 1-3 TiO2 1-4 Li2O 1-5 K2O 1-2 AI2O3 1-2 ZrO2 1-2 Fe2O3 1-2 CaO 1-2 Table 2: Bismuth-based glass frit composition Component Mol (%) SiO2 40-50 Bi2O3 30-60 B2Os 10-20 Li2O 5-10 ZrO2 1-5 Al2O3 1-5 K2O 1-2 MgO 1-2 CaO 1-2 The resulting enamel compositions consist mainly of glass frit, a colorant, and an organic medium such as the medium of the invention, exhibiting high initial adhesion strength. The glass enamels are applied to a glass substrate and then subjected to an organic oven-drying process where curing takes place. During this stage, the glass plate is exposed to physical and chemical effects such as transfer, transport, and handling. Here, thanks to the medium of the invention, the surface exhibits resistance to environmental effects. Subsequently, firing takes place, during which the enamel melts, adheres to the glass substrate, and the glass is transformed into the desired final shape. It exhibits suitable rheology, good shelf life, moderate linear expansion coefficient, good adhesion to the glass substrate, good chemical resistance, and physical durability. The viscosity values ​​of glass enamels vary depending on the application method to the glass layer, as follows: The viscosity of glass enamel suitable for roller coating is approximately 8,000 cPs - 40,000 cPs at 25°C and 10 rpm. The layer thickness after application (before drying) is between 1-150 microns. The viscosity of glass enamel suitable for screen printing is approximately 8,000 cPs - 30,000 cPs at 25°C and 10 rpm. The layer thickness after application (before drying) is between 5-100 microns. For layers created by screen printing, drying is achieved by heating to a temperature between 120-150°C (glass temperature) for approximately 2 to 5 minutes. Table 3 shows the tests applied to painted glass before heat treatment. Tests Conditions Result Color Spectrophotometer measurement ΔΕ*< 0.5 Initial adhesion strength (Green strength) TS EN 13523-4 / ASTM D3363 Determination of film hardness - Pencil test B Cross-cut (ASTM 3359-02) A plus sign is made on the painted surface with a cutting tool, tape is applied and removed 0B / 5B pH value DIN ISO 976 8-9 Density 25°C, DIN EN ISO 2811-1 0.98 g / cm3 Viscosity 25°C, Brookfield, spindle LV-64 / 12 rpm, DIN EN ISO 2555 3,000-4,000 cP Color tolerance (ΔΕ*) is used to determine color homogeneity between productions. A sample is taken once per shift, measured after heat treatment, and recorded. The goal is to achieve ΔΕ* < 2.0 both within and between campaigns. Color differences between produced plates are determined from the painted glass surface using the following formulas with parameters L*, a*, and b*. AL* = L*plate 2 - L*plate 1 Δ3* = a*plate 2 - a*plate 1 Δb* = b*plate 2 - b*plate 1 The ΔΕ* value is calculated using the following formula: ΔΕ* = [(AL*)2 + (Aa*)2 + (Ab*)2]1 / 2 Table 4 presents the results of the comparison of water-cleanability, initial adhesion strength, and color values ​​among the prepared glass enamels. Table 4: Comparison results between the prepared glass enamels. Example Water washability Initial adhesion strength Color values ​​Bi-based black Very good Very good ΔΕ<0.5 Bi-based white Very good Very good ΔΕ<0.5 Zn-based black Very good Very good ΔΕ<0.5 Zn-based white Very good Very good ΔΕ<0.5 High initial adhesion strength mediums and compositions containing them have a wide range of applications. The high initial adhesion strength medium described in this invention can be used to create decorative and functional coatings for glass, porcelain, and other surfaces (substrates). These decorative coatings include those that form glass or glass-ceramic coatings. TS EN 13523-4 / ASTM D3363 Determination of film hardness - Pencil test This experiment involves determining the pencil hardness of an organic coating (enamel prepared with frit, pigment, and the medium subject to this invention) on a glass surface after oven drying, using pencils of known hardness. The study range is based on pencil hardness. Soft pencils: HB, B, 2B, 3B, 4B, 5B, 6B Hard pencils: F, 2H, 3H, 4H, 5H, 6H In this experiment, the surface hardness of the cured enamel film is determined from soft to hard according to a defined scale using standard hardness pencils. The hardness level, which is one level softer than the softest pencil that leaves a permanent mark on the paint surface, is determined as the pencil hardness of the film. (SOFT) 6B - 5B - 4B - 3B - 2B - B - HB - F - Η - 2H - 3H - 4H - 5H - 6H (HARD) HB-F = high initial adhesion strength (high green strength) B-2B = medium greenstrength (medium initial adhesion strength) 3B-6B = low initial adhesion strength (low green strength) This invention provides the first high-adhesion medium (coating component) containing 60% glass frit by weight on a glass surface. By applying this composition to the glass, a layer of the coating component is formed, dried, and solidified. This ensures that the glass emerging from the drying oven is resistant to physical and chemical effects. It also prevents the formation of surface defects due to any external impact. With this invention, a water-based acrylic-melamine organic carrier with high initial adhesion strength has been developed, and experimental studies have shown that the developed medium offers significantly higher initial adhesion strength compared to standard mediums. SOURCES 1. Mark R. VanLandingham, Tinh Nguyen, W. Eric Byrd & Jonathan W. Martin (2001). On the use of the atomic force microscope to monitor physical degradation of polymeric coating surfaces. Journal of Coatings Technology, 73, 43-50 (2001). 2. D. R. Bauer, R. A. Dickie (1980). Crosslinking chemistry and network structure in organic coatings. I. Cure of melamine formaldehyde / acrylic copolymer films. Journal of Polymer Science: Polymer Physics Edition, vol 18, Issue 10, p:19972014 (1980).

Claims

REQUESTS 1. Glass coating compounds, thick and thin film components, glass enamels, and other coatings. cellulose ether, surfactant, developed for use in the structure of their compositions, dispersion agent, medium containing a mixture of one or more solvents. It is an (organic carrier) and its characteristic is that it provides initial adhesion during the transportation of glass enamels. It contains acrylic resin and melamine resin to increase its strength.

2. Medium conforming to Claim 1, characterized by its composition: 10-30% acrylic resin by weight. 2-10% by weight melamine resin, 2-5% by weight cellulose ether, 10% by weight 1-3% surfactant, 1-5% dispersion agent by weight, and by weight It contains a solvent mixture in a ratio of 45-84%.

3. The medium is compliant with Claim 1 and its characteristic is; a 3:1 ratio of acrylic resin to melamine resin. It includes. 15 4. The medium conforming to Claim 1 has the property of having a viscosity of 1,000-10,000 at 25 °C and 15 rpm. It is cPs.

5. The method of producing the medium mentioned in any of the above requests is 20 feature;  Acrylic resin and melamine are added to the solvent mixture in the mixing bowl, in that order. by adding resin, cellulose ether, surfactant and dispersion agent mixing, It includes the process step.

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