A self-cleaning daily-use ceramic decal and its manufacturing method

Abstract

This invention relates to the field of daily-use ceramics technology, specifically to a self-cleaning daily-use ceramic decal and its manufacturing method. A self-cleaning daily-use ceramic decal includes, from the outside in, a photocatalytic cover adhesive layer, a pattern layer, an aqueous sol layer, and a base paper layer. The photocatalytic cover adhesive layer comprises an outer layer and an inner layer; the outer layer is a cover oil layer, and the inner layer is a mixing agent layer. TiO2 is added to the mixing agent layer. The mixing agent layer is used separately from the ink layer, which does not affect the original color of the ink or increase the thickness of the pattern. This effectively avoids wasting other additives while ensuring the desired effect.

Description

Technical Field

[0001] This invention relates to the field of daily-use ceramics technology, specifically to a self-cleaning daily-use ceramic decal and its manufacturing method. Background Technology

[0002] The most common type of ceramic decal is the small film decal, also known as water transfer decal. It involves printing the pattern onto a highly absorbent base paper pre-coated with water-soluble adhesive, then wetting it with water. The base paper absorbs the water and dissolves the water-soluble adhesive on its surface, allowing the oil-based printed pattern to separate from the water. After removing the base paper, the decal can be applied, transferring the printed pattern onto the ceramic.

[0003] TiO2 is widely used in photocatalysis due to its stable physicochemical properties, non-toxicity, lack of pollution, and low cost. TiO2 mainly exists in three crystal phases: anatase, rutile, and brookite. However, it is prone to phase transformation at high temperatures. Anatase is generally considered to be the most active crystal form, followed by rutile, while brookite and amorphous TiO2 do not exhibit significant photocatalytic activity.

[0004] In their paper "Research Progress on the Crystal Transformation of Titanium Dioxide", Fu Chunlin and Wei Xiwen pointed out that the transformation temperature of anatase TiO2 to rutile TiO2 is 610℃-915℃, and the temperature at which anatase TiO2 completely transforms into rutile TiO2 is above 1000℃.

[0005] In the published patent CN107651851B, a photocatalytic glaze for moisture-regulating ceramic tiles and its preparation method, low-temperature frit is used as the main raw material component, bentonite as the glaze suspending agent, calcium carbonate as the pore-forming agent, and anatase titanium dioxide is introduced as the photocatalyst. The raw material weight composition is: 45-55 parts low-temperature frit, 0.3-1.2 parts anatase titanium dioxide, 0.5-2 parts calcium carbonate, 0.5-2 parts bentonite, 0.5-1.5 parts dispersant, and 45-65 parts water, achieving the photocatalytic properties of the glaze. This method for preparing the photocatalytic glaze is simple, but the amount of anatase titanium dioxide used is relatively large. Furthermore, everyday ceramic tiles often have decorative decals for aesthetic purposes, which can obscure the glaze surface and thus affect the photocatalytic effect.

[0006] In the published patent CN112521142A, a photocatalytic ceramic and its preparation method, as well as a method for degrading the organic dye RhB, approximately 5-10% TiO2 in titanium extraction slag is fully utilized to prepare the photocatalytic ceramic. The main steps include grinding the titanium extraction slag to a predetermined particle size to obtain a green body powder; mixing the green body powder with a 5-8% polyvinyl alcohol solution at a mass-to-volume ratio of 10-20:1 kg / L and granulating to obtain green body granules with a particle size of 20-40 mesh; pressing the green body granules to obtain a green body; preheating the green body to remove moisture, then heating it at a heating rate of 5-15℃ / min to 1150-1200℃ and holding it at that temperature for 15-60 min, followed by cooling to obtain the photocatalytic ceramic. However, the firing temperature of daily-use ceramic glazes is generally above 1200℃. At this temperature, anatase TiO2 transforms into rutile TiO2, significantly reducing the photocatalytic effect.

[0007] Therefore, this application provides a self-cleaning ceramic decal and its manufacturing method, which solves the problem of reduced photocatalytic effect and affected product surface quality in the prior art, and improves the self-cleaning function of ceramic decals for decorating daily ceramics. Summary of the Invention

[0008] To address the aforementioned problems, this invention provides a self-cleaning daily-use ceramic decal and its manufacturing method.

[0009] The technical solution adopted by the present invention to solve its technical problem is: a daily ceramic decal with self-cleaning function, comprising a photocatalytic cover adhesive layer, a pattern layer, an aqueous sol layer and a base paper layer arranged sequentially from the outside to the inside, wherein the photocatalytic cover adhesive layer comprises an outer layer and an inner layer, the outer layer being a cover oil layer and the inner layer being a mixture layer.

[0010] As an optimization, the mixture layer is composed of a coating oil, a co-solvent, and TiO2 powder mixed in a ratio between 200:100:3 and 40:20:3.

[0011] As an optimization, the particle size of the TiO2 powder is less than 80 nm.

[0012] As an optimization, the co-solvent is one or more of potassium oxide, sodium oxide, calcium oxide, magnesium oxide, zinc oxide, lithium oxide, boron oxide, and barium carbonate.

[0013] A method for producing daily-use ceramic decals with self-cleaning function, used to prepare the daily-use ceramic decals described in any one of the above-mentioned methods, comprising the following steps:

[0014] A1. Design and layout of the decal patterns;

[0015] A2. Print the designed pattern onto the base paper with a water-based adhesive layer;

[0016] A3. Spray the prepared mixture onto the pattern surface, and finally spray the cover oil;

[0017] A4. After drying, you will get daily-use ceramic decals with self-cleaning function.

[0018] As an optimization, the mixture in step A3 includes a cover oil, a co-solvent, and TiO2 powder in a ratio of 200:100:3 to 40:20:3.

[0019] This invention relates to a self-cleaning daily-use ceramic decal and its manufacturing method, which has the following advantages:

[0020] The daily ceramic decal of this application contains a mixing layer, which is used separately from the ink. This does not affect the original color of the ink, nor does it increase the thickness of the pattern. While ensuring the effect, it effectively avoids the waste of other additives.

[0021] Adding a co-solvent enhances the adhesion of TiO2 particles to the patterned surface, preventing them from falling off.

[0022] The manufacturing method described in this application effectively prevents the transformation of TiO2 from the anatase phase to the rutile phase at the color-baking temperature (around 800℃), ensuring the photocatalytic effect of anatase TiO2. Special modified TiO2 particles are used to ensure that anatase TiO2 functions effectively under visible light. This method effectively prevents decals from obscuring the glaze and reducing the self-cleaning effect, and the effect is more pronounced in daily-use ceramic products with full-surface decoration. The manufacturing process is simple, highly operable, and has a broad market potential. Attached Figure Description

[0023] Appendix Figure 1 This is a schematic diagram of the structure of the daily-use ceramic decal of the present invention.

[0024] The layers are: 1. Cover oil layer, 2. Mixing agent layer, 3. Pattern layer, 4. Water-based sol layer, and 5. Backing paper layer. Detailed Implementation

[0025] like Figure 1 In the embodiment shown, a daily-use ceramic decal with self-cleaning function includes a cover oil layer, a mixture layer, a pattern layer, an aqueous sol layer, and a base paper layer arranged sequentially from the outside to the inside.

[0026] The mixture layer is composed of a coating oil, a co-solvent, and TiO2 powder mixed in a ratio between 200:100:3 and 40:20:3.

[0027] The TiO2 powder has a particle size of less than 80 nm.

[0028] The modified TiO2 powder used in this application is processed as follows: anhydrous ethanol is added dropwise to a tetrabutyl titanate solution and stirred, and a modifier is added and stirred continuously to obtain solution A; then acetic acid and water are added to anhydrous ethanol and stirred to obtain solution B, and the pH value is adjusted to 3-4.

[0029] Solution B is added dropwise to solution A while stirring, and stirring is continued for 1-2 hours to obtain a clear and transparent sol. After constant temperature aging, a transparent gel is obtained. After drying, crystals are obtained. The crystals are then ground into powder in a mortar and calcined in a muffle furnace at 600℃ for 2 hours to obtain modified titanium dioxide powder.

[0030] The modifier is one or more compounds containing ions such as copper, iron, silver, manganese, cobalt, cerium, and zinc.

[0031] The co-solvent is one or more of potassium oxide, sodium oxide, calcium oxide, magnesium oxide, zinc oxide, lithium oxide, boron oxide, and barium carbonate.

[0032] A method for producing daily-use ceramic decals with self-cleaning function, used to prepare the daily-use ceramic decals described in any one of the above-mentioned methods, comprising the following steps:

[0033] A1. Design and layout of the decal patterns;

[0034] A2. Print the designed pattern onto the base paper with a water-based adhesive layer;

[0035] A3. Spray the prepared mixture onto the pattern surface, and finally spray the cover oil;

[0036] A4. After drying, you will get daily-use ceramic decals with self-cleaning function.

[0037] The mixture in step A3 includes a cover oil, a co-solvent, and TiO2 powder in a ratio of 200:100:3 to 40:20:3.

[0038] The above-described specific embodiments are merely specific examples of the present invention. The patent protection scope of the present invention includes, but is not limited to, the product form and style of the above-described specific embodiments. Any daily-use ceramic decal with self-cleaning function that conforms to the claims of the present invention and its manufacturing method, as well as any appropriate changes or modifications made by those skilled in the art, shall fall within the patent protection scope of the present invention.

Claims

1. A method for producing daily-use ceramic decals with self-cleaning function, characterized in that: The preparation steps are as follows: A1. Design and layout of the decal patterns; A2. Print the designed pattern on the base paper with the water-based sol layer (4); A3. Spray the prepared mixture onto the pattern surface, and finally spray the cover oil; A4. After drying, you will get daily-use ceramic decals with self-cleaning function; The self-cleaning daily ceramic decal includes a photocatalytic cover adhesive layer, a pattern layer (3), an aqueous sol layer (4), and a base paper layer (5) arranged sequentially from the outside to the inside. The photocatalytic cover adhesive layer includes an outer layer and an inner layer. The outer layer is a cover oil layer (1), and the inner layer is a mixture layer (2). The mixture layer (2) in step A3 is composed of a mixture of cover oil, co-solvent, and TiO2 powder in a ratio between 200:100:3 and 40:20:3; The co-solvent is one or more of potassium oxide, sodium oxide, calcium oxide, magnesium oxide, zinc oxide, lithium oxide, and barium carbonate; The TiO2 powder processing procedure is as follows: anhydrous ethanol is added dropwise to a tetrabutyl titanate solution and stirred, and a modifier is added. Stirring is continued to obtain solution A; then acetic acid and water are added to anhydrous ethanol and stirred to obtain solution B, and the pH value is adjusted to 3-4. Solution B is added dropwise to solution A while stirring, and stirring is continued for 1-2 hours to obtain a clear and transparent sol. After constant temperature aging, a transparent gel is obtained. After drying, crystals are obtained. The crystals are ground into powder in a mortar and then calcined in a muffle furnace at 600℃ for 2 hours to obtain modified titanium dioxide powder. The modifier is one or more compounds containing ions such as copper, iron, silver, manganese, cobalt, cerium, and zinc.

2. The method for producing daily-use ceramic decals with self-cleaning function according to claim 1, characterized in that: The TiO2 powder has a particle size of less than 80 nm.

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