TW528741B - High-temperature glaze with anti-dust and anti-bacteria functions, and the preparation thereof - Google Patents

Abstract

A recipe of a high temperature glaze is prepared to have the functions of anti-dust and anti-bacteria for ceramic products. Various raw materials are used for the glaze in the present invention. The ranges for each containing chemical component in the glaze are: 40 wt% to 65 wt% of SiO2, 9 wt% to 15 wt% of Al2O3, 10 wt% to 15 wt% of CaO, 4 wt% to 8 wt% of ZnO, 2 wt% to 5 wt% of Na2O, 2 wt% to 5 wt% of K2O, 0.5 wt% to 2.5 wt% of TiO2, and 0.1 wt% to 1.8 wt% of Ag2O. The distribution of the particle size of this glaze is controlled, so that the cumulated weight percent of the particles with diameters smaller than 0.5 μm is above 50 wt%. After spraying with this specially made glaze, the ceramic products can be sintered at temperatures between 950 DEG C and 1300 DEG C. Therefore, a ceramic glaze surface sintered at high temperature with both functions of anti-dust and anti-bacteria is achieved.

Description

528741 A7 _____ B7 V. Description of the Invention (I) " '^ (1), Background of the Invention The present invention relates to a ceramic glaze that can be fired at high temperature. After the embryo, it can be calcined in the body at a high temperature for one time, and the glazed surface after calcination can have both antifouling and embryo resistance. The manufacturing method of general ceramic products, such as tableware, tiles, bathroom equipment, is to first mix, grind, shape, and sinter ceramic powder particles such as clay, feldspar, and quartz to form ceramic embryos and ceramics. Raw cup of cricket. It will faithfully reflect the roughness of the mold surface and the appearance and size of the ceramic powder used; that is, the larger the particles of the starting material, the greater the roughness of the surface. : The surface of general ceramic products will be coated with a layer of glaze (as shown in the first drawing). The main ingredients of the glaze and the raw material of the embryo body are similar; the glass of the glaze will meet more after firing. The flow of the glass phase makes the surface of the embryo body smooth and shiny (as shown in Figure 2). Coloring materials are often added to glazes, so that in addition to covering the yellowish embryos, the glaze can produce different colors and achieve beautiful appearance. However, because the raw material of glaze is the same as the powder of ceramic raw material, it must be prepared through mixing, ball milling and other steps. Therefore, the roughness of the surface of the glaze layer is also affected by the particle size of the raw material, and of course it is also affected by the roughness of the surface of the embryo In addition, during firing, the embryo body and the glaze will shrink, causing defects such as unevenness and pinholes on the surface. These uneven surfaces and pinholes will become the accumulation location of dirt and bacteria in the product during use. These dirt and bacteria will continue to accumulate and multiply, making the surface of ceramic products dirty. The paper standards are applicable to Chinese national standards (CNS ) A4 size (210X297 mm)

II! —. 1-: >!:--!-Λ 1 n I- I (Please read the notes on the back and fill in this one hundred C-Order · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 528741 A7 Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau Ⅴ. Description of the Invention (2), dirty, and often must be washed and hydrochloric acid pickled to remove dirt and bacteria, causing a lot of inconvenience. In view of this shortcoming, the market has been There are ceramic products with antifouling, and ceramic products with anti-garden. However, 'anti-fouling products are known to manufacturers by the manufacturer and are not disclosed; and antibacterial products mostly contain silver inorganic compounds and titanium dioxide particles. Titanium dioxide is a ceramic oxide with photocatalytic effect. Ultraviolet light can excite titanium dioxide to release electrons, and it can further decompose the organic substances in contact with it, making bacteria unable to breed and reproduce to achieve antibacterial effect. Inorganic compounds containing silver also They are widely used as antibacterial agents. These two kinds of antibacterial agents have been successfully used in some products, but cannot be applied at high temperature to burn them to the products. In the glaze layer of the product, or on its surface. This is because titanium dioxide will combine with the clay, clay, feldspar and other raw materials in the glaze, and then dissolve into the glass structure instead of titanium dioxide. The melting point of silver It is only 960 ° C. The vapor pressure of liquid silver is very high when sintered above 960 ° C. Therefore, it will volatilize a lot when sintered above 1000 ° C, causing the silver on the surface to volatilize; so the surface is no longer The presence of silver has lost its antibacterial function. Therefore, the current antifouling or antibacterial ceramic products on the market are first fired at high temperature, and then the antibacterial agent is applied to the surface of the glaze layer in a secondary processing method, and then at a lower temperature. Preparation by firing method causes complicated manufacturing process, high manufacturing cost, and expensive related products. (2) Description of the invention The inventor described that ceramic products must be fired at high temperature, and ceramic products (especially sanitary) Ceramics, such as toilets, washbasins, etc.) and our daily life (please read the precautions on the back before filling this page) Order d This paper size applies Chinese National Standards (CNs) Λ4 specifications (210 × 297 mm) 528741 Ministry of Economic Affairs Printed by the Consumer Affairs Bureau of the Property Bureau A7 B7 V. Invention Description (3, Living shoulders, are closely related, so the cleanliness of the surface has a great impact on the safety and health of the user. Therefore, a large amount of money has been invested for a long time. "Research" invented a new glaze formulation: this glaze can be sprayed directly on the embryo body in the traditional traditional application method, and it can be sintered with the ceramic embryo body at high temperature at one time. Then, the surface of the ceramic product is sprayed and fired, so it has the characteristics of easy construction and low manufacturing cost. The fine glazed quality after firing has a very flat roughness, which makes it difficult for general dirt to adhere to the surface. It achieves its antifouling effect. Therefore, the glaze has excellent high temperature stability and can keep the antibacterial agent, so that the antifouling glaze can have antibacterial function at the same time. (3) Detailed description of the invention. The invention is a special anti-fouling and anti-bacterial high-temperature glaze based on special glaze formula and precise raw material powder particle size control engineering. The chemical composition of glazes used in general ceramic products is very similar, but due to different uses of ceramic products (such as wall tiles, floor tiles, art ceramics, sanitary ceramics, tableware ceramics, etc.), the firing temperature in the process is different (95 ° C to 130 (TC), the heating rate and high temperature constant temperature time are also different; so the chemical composition of the glaze used in ceramic products for different uses must be adjusted slightly to fully meet its firing The conditions listed below are the chemical composition and composition ratio range they often contain: Main components: the main structural components of the glaze glass

Si02: 55 wt% (weight percent) to 75 wt //, A12〇3 ·· 5 wt ° / 0 to 10 wt //, the paper is compliant with China National Standard (CNS) A4 specifications (210X297 male 5) ------ (Please read the precautions on the back before filling in this page)-Order 74 8 2. A7 _______ __ B7 V. Description of the Invention (4)-Sub-components: Flux or opacity needed for glaze preparation Ingredient CaO: 6 wt% to 9 wt%,

Zr〇2: 3 wt% to 5 wt%,

ZnO: 3 wt% / 0 to 5 wt% / 0, K20: 2 wt% / 0 to 3 wt%,

Na2〇: 1 wt% or less, trace ingredients: trace ingredients Mg〇: 1 wt% to 1.5 wt%, which are present in the main and auxiliary ingredients,

BaO: 0.5 wt% to 1.0 wt%, printed by the 8th Industrial Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Generally speaking, in the traditional ceramic industry glazing process, firstly spray the general glaze slurry on the surface of the ceramic body (such as (Shown in Figure 1), the thickness of the glaze layer must be controlled between 0.3mm (mm) and 0.5mm according to the requirements of the ceramic industry process to achieve its shielding effect on the color of the ceramic body. Moreover, the raw materials of the glaze slurry used in the ceramic industry process must undergo a honing process to control its particle size distribution (as shown in Figure 3), and the cumulative weight of those whose particle diameter is less than 10 μm (micron, m) is often required. Cumulative weight percentage (wt%) must be controlled between 75wt% and 85wt%; under this condition, the glaze slurry is sprayed on the ceramic embryo body and fired at high temperature (950 ° C to 130 (TC) After it is finished, the roughness of the glassy glazed surface can reach a smoothness acceptable to the average consumer (the average roughness is about 0.3 μm to 0.6 μm). One of the characteristics of the glaze according to the present invention is that Among them, the proportion of the content of various chemical compositions must be adjusted so that it conforms to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) and the scale of the paper used in the general ceramic manufacturing process. Print A7 ______ B7 _ V. Description of the invention (5). The softening point temperature should be lower than that of ordinary glazes commonly used with it by about 10.0 to 30. (3, due to the use of the product and Process The difference will be different. Basically, if the sintering process is performed at a higher temperature, the difference in the softening point temperature between the two will need to be appropriately enlarged in order to obtain a more detailed glaze quality, and provide a surface to prevent ceramic products The method for contaminating the glaze layer is to have anti-fouling function. Furthermore, if a commercially available high-temperature antibacterial agent containing silver is added to the glaze of the present invention (product name: AM15, manufacturer: Japan Sumitomo Osaka Cement Co., Ltd.) Co., Ltd. 'is prepared into an antifouling glaze paddle containing silver antibacterial agent. The amount of antibacterial agent added ranges from 0.1% to 10% by weight, depending on factors such as firing conditions and product use. Then, this is determined. The glaze award is sprayed on the glaze surface that has been sprayed with the general glaze slurry. When this surface is sprayed with the antifouling glaze slurry containing silver antibacterial agent, the embryo body is fired once in a kiln at high temperature, which will make the ceramics. The surface glaze layer of the product has both antifouling and antibacterial functions. The following is the antifouling and antibacterial glaze of the present invention, which is obtained by adjusting the appropriate raw materials based on ceramic products that meet different applications and their firing conditions. Chemical composition and composition ratio range: Main ingredients: Si〇2: 40 wt% to 65 wt%, Al203: 9 wt% to 15 wt% / Ca, CaO: 10 wt% to 15 wt% / 0, Sub-components: ZnO: 4 wt% to 8 wt ° / 〇, Na20: 2 wt% to 5 wt%, the paper ruler's degree applies to China National Standard (CNS) A4 specification (210X 297 mm) (please read the back first) Please note this page before filling in this page) r ··, \ = u 74 8 2 5 A7 B7 V. Description of the invention (6) 'K2〇: 2 wt% to 5 wt%,

Ti〇2: 0.5 wt0 / 〇 to 2.5 wt〇 / 〇,

Ag20: 0.1 wt% / 0 to 1.8 wt% / 0. The present invention also utilizes a precise surface roughness control project to provide a method for enhancing its prevention of surface contamination. As mentioned before: the roughness of the glaze layer surface of ceramic products will be affected by the particle size of the raw material powder, as well as the roughness of the surface of the embryo body. The particle size distribution of the raw materials of the glaze medicine of the present invention is required to be a cumulative weight percentage of a pine with a diameter of less than 0.5 μm, which must be controlled to more than 50% by weight (as shown in Figure 4). Before the ceramic green body sprayed with general glaze slurry is fired at high temperature, if the glaze slurry of the present invention is sprayed on the surface (as shown in FIG. 5), the glaze can be improved after firing. The roughness and average roughness of the surface can be reduced to a fine degree between 0.05 μm and 0.20 μm. The thickness of the glaze layer must be controlled between 0.05mm and 0.10mm. The thickness of the glaze layer can be controlled by adjusting the glaze slurry concentration to meet the requirements. In this way, the special glaze of the present invention can be simultaneously fired at a high temperature with the glazed embryo body, so that the surface glaze layer of the ceramic product can obtain more detailed glaze quality; so that general dirt will not easily adhere to its surface And achieve its antifouling effect. Also, because the glaze of the present invention contains a silver antibacterial agent, the surface glaze layer of the fired ceramic product also has an antibacterial function. Therefore, ceramic products produced according to this glaze formulation and manufacturing process can be called glaze ceramics with antifouling and antibacterial functions. The progress of the present invention can be demonstrated by the following examples: nil-1ί---n-(Please read the notes on the back before filling out this page) Order the Intellectual Property Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives to print this standard for China ) 8 rules ^ (210X 297 mm) ^ 528741 Μ * "--~ ~ ~ B7 V. Description of the invention (Y ^ ~ -----~~ Example 1: 'H stomach control example) basis A batch of white ceramic glazes is prepared for the needs of the inter-process, and the materials of each side (such as kaolin, feldspar, sand, ...) are adjusted by proportions so that it contains the following chemical composition:

Si0 2 • 70.6% by weight, ai2O3 • 9.2% by weight, CaO • 7.6% by weight, Zr0: 3.5% by weight, ZnO ·· 3.55% by weight, K2 ·· 2.5% by weight, Na2〇: 0.9wt〇 / 〇, Mg〇 ·· 1 · 3wt%, Ti〇2 ·· 0.035 wt% BaO: 0.8wt% 〇 (Please read the notes on the back before filling this page) The raw materials for the above-mentioned glaze medicine printed by the consumer cooperative are prepared through mixing, water addition, ball milling and other steps, and the particle size distribution is controlled so that the cumulative weight percentage of the raw material powder particles whose diameter is less than 10 μηι accounts for 82wt%. The glazing slurry was spray-coated on the ceramic body under this condition, and the thickness of the glaze layer was about 0.46 mm. After firing at a high temperature of 1220 ° C, a glassy white glazed surface was produced; measured by a surface roughness meter , Its average roughness is 0.32 μm. Atomic force microscope (AFM) was used to check the surface quality. The test results are shown in Figure 6. This paper size applies to Chinese National Standard (CNS) A4 (210X29? Mm) __ 528741 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (8) Example 2: Hang stain, antibacterial ceramic glaze The surface production is the same as the preparation process in Example 1. The various raw materials are adjusted through proportions, and then the powder size control project is performed using a suitable honing equipment, so that the obtained glaze slurry has 92 wt% of raw materials. The particle diameter is less than 0.5 μm. Before the glaze slurry is discharged from the honing equipment, add the silver-containing antibacterial agent to it, and then hob it again for about 1 hour to achieve complete uniform dispersion (the detailed preparation process is shown in Figure 7). The chemical composition of the prepared glaze paste is as follows: Si02: 60.6wt%, Al203: 13.3wt%, CaO: 13.8wt%, ZnO: 4.6wt% 〇κ2ο: 2.3wt% 5 Na20 3.2wt%, Ti02: 1 · 1 wt%, MgO: 0 · 1 wt%, BaO: 0.2wt%, Ag20 ·· 0-8wt%, this glaze slurry was sprayed on the already coated Example 1 On the ceramic body of the white glaze slurry, the thickness of the glaze layer is about 0.06 mm, and the same is fired at a high temperature of 1220 ° C. The surface quality of the ceramic glaze fired under this process condition is quite fine. Inspection using surface roughness meter and atomic force microscope 'found that the average roughness of € was only 0.12 μηι, and the test results of atomic force microscope I ---.-- r --- ¾ clothing ------, order I ------ 0 f Please read the notes on the back before filling in this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 528741 A7 B7 V. Description of the invention (?) Example 3 shown in Figure 8: (Please read the precautions on the back before filling this page) Ceramic Glaze Pencil Scratch Test 1 Use the glaze prepared in Examples 1 and 2 to make a test ceramic glaze. First, the general glaze of Example 1 was sprayed on the flat ceramic surface, and then the antifouling and antibacterial glaze prepared in Example 2 was sprayed on the right half of the glazed surface, and then fired. In order to compare the difference in surface roughness between the left and right ceramic glazed surfaces, in addition to the atomic force microscope test, a medium-hard pencil (HB) is used to continuously scratch the surface of the glazed layer. The results of this test can be found in Section 1. 9 Figure. Because the ceramic glaze applied with general glaze is relatively rough, it will cause wear of the pencil core and leave obvious marks; while the glaze applied with antifouling and antibacterial glaze is quite smooth, there are no traces of pencil core, it is not easy to verify it again. The thoughts attached to the dirt. Example 4: Ceramic toilet glazed flush test. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the glazing method according to Example 3 to produce a batch of left and right halves of ceramic toilets with different glazed surfaces (such as No. 10). As shown). A fatty acid similar to human excrement plus a black pigment was used to prepare a stain-like stain ' and brushed on the inside surface of the toilet to conduct a flushing test. The test results showed that the antifouling and antibacterial glazed surface (right half) was rinsed with water, and the dirt imitating human excrement immediately detached from the smooth surface. In contrast, the surface quality of the left half is coarser, and it is easy to be adsorbed by dirt. The scale of the paper is applicable to the Chinese National Standard (CNS) A4 specification (21〇 > < 297 mm). Printed by the Consumers ’Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Α7 Β7 5. Description of the invention (丨 〇) It is not easy to eliminate. Example 5: Ceramic surface antibacterial test ... Flower in the urinal-now: & The Jg test was applied with the glaze prepared in Example 1 and Example 2, respectively, sprayed on the flower in the urinal (such as the 11th (Shown in the figure), the sample was fired for antibacterial test. They were placed in urinals in frequently used public toilets for urine and bacteria control tests. After three months of continuous use without washing, inspecting the sample, it was found that the antifouling and antibacterial ceramic glaze exerted its antibacterial effect, and only a few stains were adhered to the surface. In general: the ceramic glaze of the glaze was covered with orange Urine stains. In order to make the ceramic products made with the antifouling and antibacterial glazes of the present invention obtain the trust and acceptance of consumers, a sample batch of antifouling and antibacterial glazes prepared by spraying ceramic embryos prepared in Example 2 was used. Entrusted with credible test certification units `` Japan Food Research Laboratories '' and `` Taiwan Food Industry Development Research Institute '' to perform antimicrobial evaluation tests, the test results report of the two (see annex 1 and 2) show that the ceramic glaze made of the antifouling and antibacterial glaze of the present invention has a bacterial reduction rate of 99.99% or more, which is qualified. The antibacterial force evaluation method and its calculation formula (as shown in Figure 12) adopted by the above two antibacterial test units are based on the "Antibacterial Activity Test Method I of Antibacterial Products" issued by the Japan Antibacterial Association, 1998 edition (Antibacterial activity test method I of antibacterial product, 1998 term version) " Fortunately, China National Standard (CNS) A4 specification (210: χΓϋmm) ~~ '> (Please read the precautions on the back before filling this page)

74 8 512 A7 B7

____ ^ ~ '— — — — ________ ___________ M Description of the Invention (丨 I), to conduct antibacterial evaluation test. The manufacturing process of the ceramic products in the above embodiments is the application of the most well-known manufacturing techniques of ceramics. Therefore, the modulation conditions of the ceramic glaze and glaze slurry disclosed in this case are suitable for mass production in the industry, and have practical economic value. Conditions for applying for an invention patent. Various changes and modifications made according to the characteristics and spirit of the scope of application of the present invention are all covered by the present invention. Figure 1. General ceramic glaze sprayed on the embryo. Fig. 2. After the ceramic body sprayed with glaze is burned at high temperature, air bubbles remain in the glaze layer. Figure 3, the particle size distribution curve of general ceramic glaze powder. Figure 4: Powder particle size distribution curve of antifouling and antibacterial glaze. Fig. 5 shows the antifouling and antibacterial glaze sprayed on the glazed embryo body. Figure 6. Atomic force microscopy results of glazed ceramics sprayed with ordinary glazes after high temperature firing. Printed by the Consumer Cooperatives of the 1st Bureau of Smart Finance, Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Figure 7: Preparation process of antifouling and antibacterial glaze. Fig. 8 shows the results of atomic force microscopy of the glazed surface of ceramics sprayed with antifouling and antibacterial glaze after high temperature firing. Figure 9. Results of pencil scratch test. Figure 10. Toilet glazed flushing test. Figure 11: Glazed antibacterial ability test ... Field test of flower in urinal. Figure 12: Simple schematic diagram of the antibacterial test method for antibacterial test and its paper size. Applicable to China National Standard (CNS) A4 (21〇 × 297mm) 74 8 A7 B7 V. Description of the invention (丨 2) -Calculation formula. Attachment 1. Anti-fouling and anti-bacterial ceramic glaze embryos, Japan Food Research Laboratories commissioned a copy of the test report of the anti-bacterial test, showing a bacterial reduction rate of 99.99% or more, which is qualified. (A total of 3 pages) Attachment 2. Anti-fouling and antibacterial ceramic glaze embryos. Entrusted Taiwan Food Industry Development Co., Ltd. with a copy of the commissioned test report of the antibacterial test. (A total of 2 pages) (Please read the notes on the back before filling this page) -Order 4 Intellectual Property Bureau of the Ministry of Economy B (printed by the Industrial and Consumer Cooperatives) This paper applies the Chinese National Standard (CNS) A4 specification (210X 297) %)

Claims (1)

528741 A8 B8 C8 D8 cavity, patent application range U __ „— 1. A high-temperature ceramic glaze with both antifouling and antibacterial functions, which is characterized in that after the glaze is formulated, various chemical components in its raw materials and their content ratio are Si 〇2 (silicon oxide) 40wt% to 65wt%, Al203 (alumina) 9wt% to i5wt%, CaO (calcium oxide) 10wt% to 15wt%, ZnO (zinc oxide) 4wt% to 8wt ° / 〇 , Na20 (sodium oxide) 2wt% to 5wt%, K20 (potassium oxide) 2wt% to 5wt%, Ti02 (titanium dioxide) 0.5wt% to 2.5wt%, Ag20 (silver oxide) 0.1wt% to i.8wt% The particle size distribution of the raw materials is that the cumulative weight percentage of those whose particle diameter is less than 0.5μm is controlled to more than 50% by weight. 2. A method for manufacturing a ceramic glaze with antifouling and antibacterial functions at the same time, which is characterized by the general ceramic industry The coating method is to spray the ceramic glaze described in the first patent application scope on the ceramic body and fire it once at a high temperature of 95 ° C to 1300 ° C, which can make the surface of the ceramic product glaze layer anti-fouling at the same time. And antibacterial function 3. A kind of concurrently manufactured product made by the manufacturing method as described in item 2 of the scope of patent application Ceramic glazed surface with anti-stain and anti-bacterial function, the average surface roughness Ra of the glazed surface is from 0.05 μm to 0.20 μm. (Please read the precautions on the back before filling this page), and the national standards are applicable to the Ding scale ( CNS) Λ4 size (210 × 297 cm) 528741 Figure 1 After firing Brother 2 Figure