KR20220063748A - Ware and preparation method of same - Google Patents

Abstract

The present application relates to ceramic ware and a manufacturing method thereof. It relates to ceramic ware and a manufacturing method thereof. Sanitary ceramic ware containing zirconium particles is pretreated with an etchant, and then a hydrophilic coating layer is formed to improve antifouling and abrasion resistance. Surface roughness and gloss is maintained through the control of an etching treatment process.

Description

Pottery and its manufacturing method {WARE AND PREPARATION METHOD OF SAME}

This application claims the benefit of the filing date of Korean Patent Application No. 10-2020-0149212 filed with the Korean Intellectual Property Office on November 10, 2020, the entire contents of which are incorporated herein by reference.

The present application relates to a pottery and a method for manufacturing the same, and after pre-treating sanitary pottery containing zirconium particles with an etching solution, a hydrophilic coating layer is formed to improve antifouling and abrasion resistance, and surface roughness and gloss through control of the etching process It's about how you can keep it.

Sanitary ware such as washbasins and toilet bowls, which are bathroom interior products, easily generate scale due to a humid environment, and antifouling functionality is required to prevent it.

If the surface of these products is made super-hydrophilic with a water contact angle of less than 15° by applying a super-hydrophilic coating, the formation of scale is suppressed due to self-cleaning by flowing water, and the generated contaminants can be easily removed.

However, during the manufacturing and handling process of sanitary ware products, various inorganic and organic contaminants are adsorbed to the surface, reducing the effectiveness of the hydrophilic surface treatment agent.

Various methods have been proposed to solve this problem, but research on a method capable of simultaneously improving anti-fouling performance and improving abrasion resistance has not been conducted, and it is time to study a method that can implement this effect.

An exemplary embodiment of the present application is to provide a pottery having improved initial quality and durability by micro-etching the surface of the pottery with an etchant to increase the bonding area between the surface of the pottery and a hydrophilic compound, and a method for manufacturing the same.

An exemplary embodiment of the present application is a pottery comprising a glaze layer containing zirconium particles, wherein the surface of the pottery includes a region in which the zirconium particles protrude from 10 nm to 50 nm with respect to the surface of the glaze layer, Analysis of the surface of the pottery by X-ray photoelectron spectroscopy (XPS) provides a pottery having a peak present at 158 eV to 175 eV.

An exemplary embodiment of the present application comprises the steps of preparing a pottery comprising a glaze layer containing zirconium particles; etching the surface of the pottery with an etchant; and applying a coating composition on the etched surface of the pottery and then curing it.

According to an embodiment of the present application, when the glaze surface of the pottery is etched by an etchant to form a fine concavo-convex structure, contaminants adsorbed on the surface are removed and at the same time, a hydroxyl group (-OH group) is activated on the surface to activate a hydrophilic compound can increase the bonding area of

According to an embodiment of the present application, it is possible to provide a ceramic product with improved antifouling performance.

According to an embodiment of the present application, it is possible to provide a ceramic with improved abrasion resistance.

1 is a schematic diagram showing before and after an etching process according to an exemplary embodiment of the present application.
2 is a flowchart illustrating an etching and coating method according to an exemplary embodiment of the present application.
3 is an SEM image of Example 1, Comparative Example 1, and Comparative Example 3.
4 is an SEM image of Example 1, Comparative Example 1, and Comparative Example 3.
5 is an SEM image of Example 1 and Comparative Example 1 and an image obtained by measuring the surface roughness.
6 is an EDS mapping result image of Example 2.
7 is an AFM image of Example 1, Comparative Example 1, and Comparative Example 3.
8 is a diagram showing the protrusion height of zirconium particles in a specific area of the AFM image of Example 1.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that the features, components, etc. described in the specification are present, and one or more other features or components may not be present or may be added. Doesn't mean there isn't.

That is, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

In the present application, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

In general sanitary ware products, various inorganic and organic contaminants are adsorbed to the surface during manufacturing and handling, thereby reducing the effectiveness of hydrophilic surface treatment agents.

In order to solve this problem, the present application has completed a pretreatment process that improves initial quality and durability by micro-etching the surface of sanitary ware with an etching agent to increase the bonding area between the surface of the porcelain and the hydrophilic compound.

When the glaze surface of the sanitary ware is etched by the etching treatment agent to form a fine concavo-convex structure, the contaminants adsorbed to the surface are removed and at the same time, hydroxyl functional groups (-OH groups) are activated on the surface to increase the binding area of the hydrophilic surface treatment agent. Therefore, it is possible to manufacture antifouling coated sanitary ware with improved superhydrophilicity, improved antifouling performance, and excellent abrasion resistance.

On the other hand, if unevenness is excessively generated on the glaze surface of the sanitary ware due to the excessive etching process, the luster of the sanitary ware product may decrease, and contaminants may be easily adsorbed. In addition, if the etching treatment is excessive, more zirconia pigment particles are exposed on the glaze surface, and the zirconia has low reactivity with the hydrophilic surface treatment agent, so the hydrophilic performance may decrease. Therefore, as will be described later, in the present application, the surface roughness and gloss of the sanitary ware product can be maintained by controlling the time and the concentration of the etching solution in the etching process.

Hereinafter, the pottery of the present application and a manufacturing method thereof will be described in detail with reference to the accompanying drawings. However, the accompanying drawings are illustrative, and the scope of the pottery of the present application and its manufacturing method is not limited by the accompanying drawings.

1 is a schematic diagram showing before and after an etching process according to an embodiment of the present application.

Specifically, Fig. 1 (a) shows the surface of a typical pottery, and the zirconium particles 13 are mostly buried in the glaze 11, and even when protruding, only a very small degree protrudes. On the other hand, FIG. 1 (b) shows the surface of the ceramic 1 etched according to an exemplary embodiment of the present application, and the glaze 11 is etched to remove the zirconium particles 13 from the glaze 11. It exists in an appropriately protruding structure.

One aspect of the present application relates to pottery.

An exemplary embodiment of the present application is a pottery comprising a glaze layer containing zirconium particles, wherein the surface of the pottery includes a region in which the zirconium particles protrude from 10 nm to 50 nm with respect to the surface of the glaze layer, Analysis of the surface of the pottery by X-ray photoelectron spectroscopy (XPS) provides a pottery having a peak present at 158 eV to 175 eV.

The pottery is not particularly limited, but is a general sanitary pottery and may include, for example, a bathroom interior product such as a washbasin, a toilet, and the like.

In particular, it is intended to include a glassy glaze layer containing zirconium pigment particles on the surface. Zirconium is a lustrous, grayish-white, hard transition metal similar to titanium. Zirconium is mainly produced as zircon and has strong resistance to corrosion. It is resistant to corrosion and has a small neutron cross-sectional area.

The zirconium particles included in the glaze layer may include Zr and Si elements, specifically ZrSiO ₄ .

The glaze layer may include SiO ₂ .

The composition of the element can be confirmed using SEM and EDS.

In the exemplary embodiment of the present application, the surface of the pottery includes a region in which the zirconium particles protrude from 10 nm to 50 nm with respect to the surface of the glaze layer. Specifically, it may include a region protruding from 15 nm to 50 nm, protruding from 15 nm to 45 nm, or protruding from 20 nm to 50 nm, and more specifically, it may include a region protruding from 30 nm to 45 nm. can

In an exemplary embodiment of the present application, the zirconium particles protrude from 10 nm to 50 nm based on the surface of the glaze layer. Specifically, it protrudes from 15 nm to 50 nm, or protrudes from 20 nm to 50 nm, and more specifically protrudes from 30 nm to 45 nm.

The lower limit of the protrusion height of the zirconium particles may be 10 nm, 12 nm, 14 nm, 15 nm, 18 nm, 20 nm, 22 nm, 25 nm, 28 nm or 30 nm, and the upper limit is 50 nm, 48 nm, 46 nm, 45 nm, 44 nm, 43 nm, 42 nm, 41 nm or 40 nm.

When the zirconium particles protrude within the above range, since the hydroxyl functional group (-OH group) is easily activated on the surface, the bonding area with the hydrophilic surface treatment agent is increased, and the hydrophilic coating itself becomes easy. Accordingly, it is possible to provide an antifouling coated sanitary ware having improved antifouling performance and excellent abrasion resistance by increasing the superhydrophilicity of the pottery.

On the other hand, when the degree to which the zirconium particles are exposed is excessively large, that is, when excessively etched surface irregularities occur, the gloss of the product is rather reduced, and the adsorption of contaminants may easily occur. If the etching treatment is excessive, more zirconia pigment particles are exposed on the surface of the glaze, but zirconia has a low reactivity with hydrophilic compounds, so the hydrophilic performance may decrease. On the other hand, if the degree to which the zirconium particles are exposed is too small, the contaminants adsorbed to the surface cannot be removed, and the hydroxyl group (-OH group) is activated on the surface, thereby increasing the bonding area of the hydrophilic compound.

The protrusion height of the zirconium particles may be measured using atomic force microscopy (AFM). AFM is a method of measuring the microscopic shape of the surface while scanning a probe attached to the tip of a small rod with a size of several tens of μm close to the sample surface. Specifically, the SII Nanocute device of SII NanoTech can be used. AR5-NCHR-10 is mounted as a cantilever, DFM, non-contact mode is set as the measurement mode, and the microscopic shape of the surface of a pottery with a size of 10×10um ² is measured with an accuracy of 1024/512 pixels/lines and zirconium. The protrusion height of the particle can be measured.

In the present specification, the protrusion height of the zirconium particles means the height from the surface of the glaze layer to the uppermost end of the zirconium particles.

At this time, the surface of the glaze layer as a reference is based on the middle value between the lowermost and uppermost ends of the glaze layer located within a radius of 1 μm from the center of the zirconium particles in the AFM image.

In the exemplary embodiment of the present application, the average particle diameter of the zirconium particles protruding from the surface of the glaze layer may be 0.1 μm to 2 μm.

In another exemplary embodiment of the present application, the average particle diameter of the zirconium particles protruding from the surface of the glaze layer may be 0.3 μm to 1 μm, specifically 0.3 μm to 0.6 μm, and more specifically 0.45 μm. there is.

In the present specification, the average particle diameter means the equivalent particle diameter of the particles protruding from the surface (equivalent 　 circular diameter). Specifically, since zirconium particles may be irregularly shaped amorphous particles, the average particle diameter is calculated based on the equivalent circular diameter assuming it is a spherical particle having the same cross-sectional area.

In the present specification, the average particle diameter can be calculated after separating the particle portion from the AFM observation image of the sample surface and measuring the cross-sectional area with image analysis software (LAS, Leica Application Suite).

In an exemplary embodiment of the present application, the pottery is 1% to 50% of the diameter of the zirconium particles, the pottery including the protruding irregularities to the surface; and a hydrophilic coating layer formed on the surface on which the zirconium particles protrude.

In this case, the diameter of the zirconium particles may mean an average particle diameter calculated based on the equivalent particle diameter of the zirconium particles protruding from the surface.

In general, the diameter of the zirconium particles may be 0.1 μm to 2.0 μm, and the height of the unevenness protruding through the etching process according to the present application may be 10 nm to 50 nm, 15 nm to 50 nm, or 20 nm to 50 nm nm, or between 30 nm and 50 nm.

In an exemplary embodiment of the present application, the pottery includes irregularities in which 1% to 50% of the zirconium particles protrude to the surface based on the diameter.

The zirconium particles may be spherical particles, but may be irregularly shaped particles, and the shape is not particularly limited. Concavities and convexities derived from 1% to 50% of the diameter of the zirconium particles in a direction perpendicular to the surface of the pottery may be formed.

If the degree to which the zirconium particles are exposed is excessively large, the etching is excessive and surface irregularities occur. On the contrary, the gloss of the product may decrease and the adsorption of contaminants may easily occur. If the etching treatment is excessive, more zirconia pigment particles are exposed on the surface of the glaze, but zirconia has a low reactivity with hydrophilic compounds, so the hydrophilic performance may decrease. On the other hand, if the degree to which the zirconium particles are exposed is too small, the contaminants adsorbed to the surface cannot be removed, and the hydroxyl group (-OH group) is activated on the surface, thereby increasing the bonding area of the hydrophilic compound.

However, the lower limit may be 1%, 5%, 15%, 20%, or 25%, and the upper limit may be 50%, 45%, 40%, 35%, or 30%. Through appropriate exposure within this range, excellent antifouling performance and abrasion resistance can be realized, and deterioration of surface roughness and gloss can be prevented.

Also, the zirconium particles may protrude from 10% to 50% of the area of the pottery. That is, the area of the protruding zirconium particles may be 10% to 50% of the total area of the pottery.

If etching occurs on an excessively large surface, the gloss of the product is also reduced, and the adsorption of contaminants may easily occur. If the etching treatment is excessive, more zirconia pigment particles are exposed on the surface of the glaze, but zirconia has a low reactivity with hydrophilic compounds, so the hydrophilic performance may decrease. On the other hand, when the etching occurs only on a narrow surface, contaminants adsorbed on the surface cannot be removed, and a hydroxyl group (-OH group) is activated on the surface, thereby increasing the bonding area of the hydrophilic compound does not occur.

However, the lower limit may be 10%, 13%, 16%, 19%, 22%, 25%, 28% or 31%, and the upper limit may be 50%, 47%, 44%, 41%, 38%, 35% or 32%. Through appropriate exposure within this range, excellent antifouling performance and abrasion resistance can be realized, and deterioration of surface roughness and gloss can be prevented.

In an exemplary embodiment of the present application, in the image of the surface of the pottery measured by AFM, 10% or more of the zirconium particles protruding from the surface of the glaze layer may have a protrusion height of 10 nm to 50 nm. In another exemplary embodiment, 20% or more, 30% or more, 40% or more, or 50% or more of the zirconium particles protruding from the surface of the glaze layer may have a protrusion height of 10 nm to 50 nm.

In an exemplary embodiment of the present application, when the surface of the pottery is analyzed by X-ray photoelectron spectroscopy (XPS), a pottery having a peak present at 158 eV to 175 eV is provided.

Photoelectron spectroscopy (XPS) is a method that can measure the binding energy of electrons by measuring the kinetic energy of the emitted electrons after emitting electrons of an element of an analysis sample using X-rays as a light source. It is an analysis method that can obtain elemental information, quantify using the area ratio of the peaks, or obtain information about the bonding chemical state from the energy shift of each peak.

In the present application, the spectrum by photoelectron spectroscopy was performed using X-ray photoelectron spectroscopy equipment (manufacturer: Thermo Fisher Scientific, model name: K-Alpha+), under the condition of an energy step of 0.1 eV and an X-ray measurement size of 150 μm. can be measured

In the exemplary embodiment of the present application, when the surface of the pottery is analyzed by X-ray photoelectron spectroscopy (XPS), it has a peak present at 158 eV to 175 eV. In another exemplary embodiment, it has a peak present at 162 eV to 174 eV, and a peak present at 166 eV to 173 eV. The peak in the above range means the S 2p peak, and the pottery in which the peak appears has excellent abrasion resistance and antifouling properties because the hydrophilic compound containing a sulfonic acid salt imparts hydrophilicity to the surface of the pottery.

In an exemplary embodiment of the present application, when the surface of the pottery is analyzed by X-ray photoelectron spectroscopy (XPS), it has a peak present at 1,066 eV to 1,081 eV. In another exemplary embodiment, it has a peak present at 1,070 eV to 1,082 eV, and a peak present at 1,072 eV to 1,081 eV. A peak in the above-mentioned range means a Na 1s peak.

In an exemplary embodiment of the present application, when the surface of the pottery is analyzed by X-ray photoelectron spectroscopy (XPS), it has a peak present at 95 eV to 110 eV. In another exemplary embodiment, it has a peak present at 98 eV to 108 eV, and a peak present at 100 eV to 106 eV. A peak in the above-mentioned range means a Si 2p peak.

In an exemplary embodiment of the present application, when the surface of the pottery is analyzed by X-ray photoelectron spectroscopy (XPS), the detected element content (atomic%) of S is 2 atomic% to 4.5 atomic based on all detected elements %am. In another exemplary embodiment, 2 atomic% to 4 atomic%, or 2 atomic% to 3 atomic%, or 2.5 atomic% to 3 atomic%. When the element content of S is included in the above-mentioned range, since a sufficient amount of the hydrophilic compound is introduced to the surface, abrasion resistance and antifouling properties are excellent. On the other hand, when the element content of S is smaller than the above range, there is a problem in that the hydrophilic compound is not properly introduced to the surface, so that the contact angle to water is large, and the abrasion resistance and antifouling properties are deteriorated.

In an exemplary embodiment of the present application, when the coating layer is analyzed by X-ray photoelectron spectroscopy (XPS), the lower limit of the detected element content (atomic%) of S is 2 atomic%, 2.2 atomic%, 2.4 atomic%, 2.6 atomic%, or 2.7 atomic%, and the upper limit is 4.5 atomic%, 4 atomic%, 3.5 atomic%, or 3 atomic%.

In an exemplary embodiment of the present application, the pottery includes a hydrophilic compound bonded to a surface on which zirconium particles protrude.

The hydrophilic compound is not particularly limited, but may be a compound in which a hydroxyl group (-OH group) is activated on the surface by the above-described etching to be combined with the hydrophilic compound, and may be an alkali metal salt of sulfonic acid.

The hydrophilic compound may be combined through a process of applying a coating composition containing the hydrophilic compound to the ceramic surface and then curing it.

In an exemplary embodiment of the present application, the pottery includes a hydrophilic compound provided on the glaze layer including the zirconium particles. Specifically, it may have a structure in which a hydrophilic compound is bonded to a glaze layer including zirconium particles.

The hydrophilic compound may be a compound capable of bonding to a hydroxyl functional group (-OH group) activated on the surface by the above-described etching, specifically, may be a compound containing S, and more specifically may be a sulfonate.

A structure in which the hydrophilic compound is bonded to the glaze layer including the zirconium particles can be formed by applying the coating composition including the hydrophilic compound on the glaze layer containing the zirconium particles and then curing.

In an exemplary embodiment of the present application, the pottery may include a coating layer including a hydrophilic compound provided on a glaze layer including zirconium particles.

In an exemplary embodiment of the present application, the pottery may include a cured product of a coating composition including a hydrophilic compound provided on a glaze layer including zirconium particles.

In an exemplary embodiment of the present application, the coating composition may include a hydrophilic compound, and specifically, a sulfonic acid salt.

In an exemplary embodiment of the present application, the coating composition may further include one or more from the group consisting of a radical initiator, a compatibilizer, and a solvent.

In an exemplary embodiment of the present application, the hydrophilic compound may be included in an amount of 30 to 50 parts by weight based on 100 parts by weight of the total coating composition.

The hydrophilic compound refers to a compound having a property of easily bonding with water molecules. Any compound having these properties can be applied. As an example, the hydrophilic compound may be an alkali metal salt of sulfonic acid. For example, the hydrophilic compound is 3-allyloxy-2-hydroxy-1-propane sodium sulfonate, 2-acrylamido-2-methylpropane-sodium sulfonate, 2-methyl-2-propene-1-sulfonate sodium, It may include at least one selected from the group consisting of 3-sulfopropyl acrylate potassium salt, 3-sulfopropyl methacrylate potassium salt, sodium vinyl sulfonate and 4-vinyl benzene sulfonate sodium. In a preferred embodiment of the present application, the sulfonate may be sodium 3-allyloxy-2-hydroxy-1-propane sulfonate.

In another exemplary embodiment, the hydrophilic compound may be included in an amount of 35 to 45 parts by weight based on 100 parts by weight of the total weight of the coating composition, and in another embodiment, 39 to 40 parts by weight may be included.

The lower limit of the content of the hydrophilic compound may be 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, or 39 parts by weight. . Also, the upper limit thereof may be 50 parts by weight, 49 parts by weight, 48 parts by weight, 47 parts by weight, 46 parts by weight, 45 parts by weight, 44 parts by weight, 43 parts by weight, 42 parts by weight, 41 parts by weight, or 40 parts by weight. . Within this range, it is possible to effectively impart hydrophilic performance to the surface of the ceramics.

In the exemplary embodiment of the present application, the radical initiator may be included in an amount of 0.5 to 5 parts by weight based on a total of 100 parts by weight of the coating composition.

The radical initiator induces a radical reaction of the compound to provide a surface bond between the glaze layer and the coating composition including the hydrophilic compound. Any compound having these properties can be applied. In a preferred embodiment, the radical initiator may be at least one selected from the group consisting of sodium persulfate and potassium persulfate.

In another exemplary embodiment, the radical initiator may be included in an amount of 0.8 to 1.2 parts by weight based on 100 parts by weight of the total weight of the coating composition, and in another exemplary embodiment, it may be included in an amount of 0.9 to 1 parts by weight.

The lower limit of the content of the radical initiator may be 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, or 0.9 parts by weight. Also, the upper limit thereof may be 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1.5 parts by weight, 1.3 parts by weight, 1.2 parts by weight, 1.1 parts by weight, or 1 part by weight. In this range, excellent adhesion can be imparted between the glaze layer and the cured product of the coating composition.

In an exemplary embodiment of the present application, the compatibilizer may be included in 2 to 10 parts by weight based on 100 parts by weight of the total coating composition.

Compatibilizers are added to basic plastic resins and used to exhibit desired performance and physical properties. In addition, the hydrophilic compound may be included for the purpose of preventing aggregation. Any compound having these properties can be applied. For example, an amide compound may be used as the compatibilizer, and urea may be preferably included.

In another exemplary embodiment, the compatibilizer may be included in an amount of 4 to 6 parts by weight based on 100 parts by weight of the total weight of the coating composition, and in another embodiment, 4 to 5 parts by weight may be included.

The lower limit of the content of the compatibilizer may be 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, or 4 parts by weight. In addition, the upper limit may be 10 parts by weight, 9.5 parts by weight, 9 parts by weight, 8.5 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight or 5 parts by weight. can be prevented

In an exemplary embodiment of the present application, the remainder excluding the compound included in the coating composition may be a solvent.

In an exemplary embodiment of the present application, the solvent may be included in an amount of 60 parts by weight or less based on 100 parts by weight of the total composition for coating.

A solvent is a substance that dissolves a solute as a medium for a solution. Any compound having these properties can be applied. As an example, it may include at least one selected from the group consisting of water, ethanol, and propylene glycol methyl ether.

In another exemplary embodiment, the solvent may be included in 10 to 60 parts by weight based on 100 parts by weight of the total composition for coating, and in another embodiment, 40 to 60 parts by weight, or 50 to 60 parts by weight, may be included. It may be included, or 53 to 55 parts by weight may be included.

The upper limit of the content of the solvent may be 60 parts by weight, 58 parts by weight, 56 parts by weight, or 55 parts by weight, and the lower limit thereof is 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 52 parts by weight. parts or 54 parts by weight.

In an exemplary embodiment of the present application, the solvent may be propylene glycol methyl ether (PGME, propylene glycol methyl ether), and the propylene glycol methyl ether may be included in an amount of 20 to 70 parts by weight based on 100 parts by weight of the coating composition. And, in a preferred embodiment, propylene glycol methyl ether may be included in an amount of 40 to 60 parts by weight.

In an exemplary embodiment of the present application, the coating composition may further include various additives other than the above as long as it does not affect the physical properties.

In the exemplary embodiment of the present application, the wetting agent may be included in an amount of 0.001 to 1 parts by weight or 0.001 to 0.2 parts by weight based on 100 parts by weight of the coating composition. A wetting agent may improve the coating property by lowering the surface energy of the coating composition.

In one embodiment of the present application, the wetting agent may be sodium dodecyl sulfate (Sodium Dodecyl Sulfate).

Since the coating composition contains a hydrophilic compound such as a sulfonate, the water content in the coating composition is high. A high water content means that the surface energy of the coating composition is high, and when coating on the glaze layer, the surface energy of the coating layer is higher than the surface energy of the glaze layer, so a wetting defect phenomenon occurs. In general, in order for wetting to occur easily, the surface energy of the glaze layer should be greater than the surface energy of the coating layer. Accordingly, by including a wetting agent such as sodium dodecyl sulfite to lower the surface energy of the coating composition, the surface energy of the coating layer may be lower than that of the glaze layer.

In another embodiment, the wetting agent may be included in an amount of 0.01 to 0.05 parts by weight based on 100 parts by weight of the coating composition, and in another embodiment, it may be included in an amount of 0.015 to 0.03 parts by weight, or 0.019 to 0.025 parts by weight. can

The lower limit of the content of the wetting agent may be 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.015 parts by weight, 0.016, 0.017, 0.018 or 0.019 parts by weight, and the upper limit thereof is 0.2 parts by weight, 0.15 parts by weight, 0.1 parts by weight, 0.05 parts by weight. parts by weight, 0.04 parts by weight, 0.03 parts by weight, 0.025 parts by weight, or 0.02 parts by weight.

In an exemplary embodiment of the present application, 30 to 50 parts by weight of a sulfonate salt, 0.5 to 5 parts by weight of a radical initiator, 2 to 10 parts by weight of a compatibilizer, and 0.001 to 0.2 parts by weight of a wetting agent based on 100 parts by weight of the total weight of the coating composition can do.

In an exemplary embodiment of the present application, the remainder excluding the hydrophilic compound, radical initiator, compatibilizer, and additive may be a solvent based on 100 parts by weight of the coating composition in total.

In an exemplary embodiment of the present application, in order to increase the bonding strength between the glaze layer containing the zirconium particles and the hydrophilic compound, a preliminary containing a silane compound between the glaze layer containing the zirconium particles and the coating layer containing the hydrophilic compound A coating layer may be provided.

That is, through the process of forming a pre-coating layer on the glaze layer, applying a coating composition containing a hydrophilic compound on the pre-coating layer and curing it, the hydrophilic compound is bonded to the glaze layer containing zirconium particles. can be easily formed.

The pre-coat layer may be formed by applying a pre-coating composition including a silane compound on the glaze layer and then curing the composition.

In an exemplary embodiment of the present application, the pottery may include a pre-coating layer comprising a silane compound provided on the glaze layer comprising zirconium particles and a coating layer comprising the hydrophilic compound provided on the pre-coating layer. .

In an exemplary embodiment of the present application, the pre-coating layer includes a silanol group.

In the exemplary embodiment of the present application, the preliminary coating layer includes a silane compound. One side of the silane compound has a reactive group capable of condensation reaction with the silanol group of the glaze layer, and the other side contains a radical reactive group capable of bonding with the coating layer containing the hydrophilic compound. The coating layer including the hydrophilic compound serves to chemically bond.

In an exemplary embodiment of the present application, the silane compound includes a silanol group.

In an exemplary embodiment of the present application, the pre-coat layer may be formed by curing a pre-coating composition including a silane compound. That is, the pre-coat layer includes a cured product of the pre-coating composition including the silane compound.

In an exemplary embodiment of the present application, the composition for pre-coating includes a silane compound.

In an exemplary embodiment of the present application, the composition for pre-coating further comprises at least one from the group consisting of an acid catalyst and a solvent.

Specifically, the composition for precoating may include 0.2 to 2 parts by weight of the silane compound, 0.2 to 2 parts by weight of the acid catalyst, and 90 to 99.6 parts by weight of the solvent based on 100 parts by weight of the total weight of the composition for precoating. When the above range is satisfied, the adhesion between the pre-coat layer and the glaze layer is excellent, and the bonding force between the pre-coat layer and the coating layer including the hydrophilic compound is excellent.

In the exemplary embodiment of the present application, the silane compound is condensed with a silanol group included in the glaze layer, and through this, the glaze layer and the pre-coating layer can be attached with high adhesion. The silane compound is vinylmethoxysilane, vinylethoxysilane, 3-methacroyloxypropyl trimethoxysilane, 3-methacroyloxypropyl triethoxysilane, 3-acroyloxypropyl trimethoxysilane, 3 -Aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-isocyanatepropyl trimethoxysilane, and may be at least one selected from the group consisting of 3-mercaptopropyl trimethoxysilane, but limited thereto not.

In an exemplary embodiment of the present application, the silane compound may be included in an amount of 0.5 to 1.5 parts by weight based on 100 parts by weight of the composition for pre-coating. In a preferred embodiment, 0.8 to 1.2 parts by weight may be included.

In an exemplary embodiment of the present application, the acid catalyst may be at least one selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and formic acid, but is not limited thereto.

In an exemplary embodiment of the present application, the acid catalyst may be included in an amount of 0.5 to 1.5 parts by weight based on 100 parts by weight of the composition for pre-coating. In a preferred embodiment, 0.8 to 1.2 parts by weight may be included.

In an exemplary embodiment of the present application, the solvent may be applied without particular limitation as long as it is a compound known to enable the formation of a coating composition in the art to which the present invention belongs. For example, the solvent may be at least one compound selected from the group consisting of alcohols, esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

According to a preferred embodiment of the present application, the solvent included in the composition for pre-coating may be propylene glycol methyl ether.

In an exemplary embodiment of the present application, the solvent may be included in 92 to 99.6 parts by weight based on 100 parts by weight of the composition for pre-coating. In a preferred embodiment, 96 to 99 parts by weight may be included.

The above-mentioned ceramics are excellent in antifouling performance and abrasion resistance, and the surface roughness and gloss are also not deteriorated compared to conventional products.

As an example, the contact angle of the surface to water may be 15 ° or less. As another example, the contact angle of the surface to water may be 10 ° or less. Through these components, it is possible to provide a hydrophilic property to the surface of the pottery.

In the present application, the contact angle is measured using KRUSS's mobile surface analyzer equipment. The contact angle with water is measured 5 times for 2 seconds each after dropping 2 μL of water droplet and displayed as an average, and the other two places in the sample are additionally measured and the total average is measured.

As an example, the wear resistance rating may be a 4th grade or a 5th grade.

The conditions for cleaning the toilet in a real life environment are simulated and evaluated as follows.

The friction condition is that the product specimen is immersed in water, and the surface of the product is reciprocated and rubbed with a PP (polypropylene) material size 30x40mm bathroom cleaning brush under the condition of a load of 500g and a friction width of 100mm.

The evaluation condition is to evaluate the antifouling performance of the specimen rubbed 10,000 times under the above conditions and display it in grades 1 to 5, and to determine whether the antifouling performance of grade 4 or 5 immediately after coating is well maintained even after 10,000 times of abrasion. .

As an example, the roughness of the surface of the pottery may be 0.1 μm to 0.6 μm. Specifically, it may be 0.4 μm to 0.6 μm.

In the present application, "surface roughness (Rz)" is measured using a Mitutoyo SJ-210 surface roughness meter according to standard DIN EN ISO4287 or KS B ISO4287. When the surface roughness meter is placed on the surface of the product and the measurement is started, the stylus of the meter measures the roughness profile of the product surface and calculates Rz.

Another aspect of the present application relates to a method of manufacturing a pottery.

An exemplary embodiment of the present application includes the steps of preparing a pottery including a glaze layer containing zirconium particles (S10); etching the surface of the pottery with an etchant (S20); After applying a coating composition on the surface of the etched pottery, there is provided a method for producing a pottery comprising the step of curing (S30).

2 is a flowchart for explaining a method of manufacturing a pottery according to an embodiment of the present application.

Hereinafter, a method of manufacturing a pottery which is an aspect of the present application for each step will be described.

S10: Prepare a pottery including a glaze layer containing zirconium particles.

The pottery is not particularly limited, but is a general sanitary pottery and may include, for example, a bathroom interior product such as a sink, a toilet, and the like. It is also aimed at including a glassy glaze layer containing zirconium pigment particles on the surface. Zirconium is a lustrous, grayish-white, hard transition metal similar to titanium. Zirconium is mainly produced as zircon and has strong resistance to corrosion. It is resistant to corrosion and has a small neutron cross-sectional area.

The above description may be applied to the zirconium particles and the glaze layer.

S20: The surface of the pottery is etched with an etchant.

In an exemplary embodiment of the present application, etching the surface of the pottery with an etchant may mean etching the surface of the glaze layer including the zirconium particles with an etchant.

In the exemplary embodiment of the present application, when the surface of the pottery is etched with an etchant, the zirconium particles may protrude from 10 nm to 50 nm with respect to the surface of the glaze layer.

Most of the zirconium particles are covered by the glaze layer to form a flat surface. When a hydrophilic treatment is performed on an untreated surface, there is a problem in that hydrophilic performance is deteriorated because the hydrophilic compound is not well bound. Therefore, in the present invention, by etching the surface of the pottery with an etchant, it is possible to increase the bonding property between the surface of the pottery and the hydrophilic compound, thereby increasing the hydrophilic performance. When the surface of the pottery is etched, the glaze surface of the silica component having relatively low chemical resistance is etched by the etching treatment agent, and zirconium particles having high chemical resistance are exposed to the surface to form a fine concavo-convex structure.

Through this pretreatment, the contact angle is changed as the hydrophilic part of the ceramic surface is activated. In general, the contact angle of the surface to water before pretreatment is 30 to 40°. However, after the pretreatment, the contact angle of the surface to water may be changed to 10° or less.

However, if the degree to which the zirconium particles are exposed is too large, that is, if the etching is excessive and surface irregularities are excessively generated, the gloss of the product may be reduced, and the adsorption of contaminants may easily occur. If the etching treatment is excessive, more zirconia pigment particles are exposed on the surface of the glaze, but zirconia has a low reactivity with hydrophilic compounds, so the hydrophilic performance may decrease. On the other hand, if the degree to which the zirconium particles are exposed is too small, the contaminants adsorbed on the surface cannot be removed, and the hydroxyl group (-OH group) is activated on the surface, thereby increasing the bonding area of the hydrophilic compound.

Therefore, it is preferable to etch the zirconium particles to protrude 10 nm to 50 nm from the surface of the glaze layer during etching. Specifically, the zirconium particles may protrude from 10 nm to 50 nm, 10 nm to 45 nm, or 10 nm to 40 nm based on the surface of the glaze layer.

In an exemplary embodiment of the present application, when the surface of the pottery is etched, 1% to 50% based on the diameter of the zirconium particles may be etched with an etchant to protrude to the surface.

However, the lower limit may be 1%, 5%, 10%, 15%, 20% or 25%, and the upper limit may be 50%, 45%, 40%, 35%, or 30%. Through appropriate exposure within this range, excellent antifouling performance and abrasion resistance can be realized, and deterioration of surface roughness and gloss can be prevented.

In the exemplary embodiment of the present application, when the surface of the pottery is etched with an etchant, the zirconium particles may protrude from 10% to 50% of the area of the pottery. That is, the area of the protruding zirconium particles may be 10% to 50% of the total area of the pottery.

If etching occurs on an excessively large surface, the gloss of the product is also reduced, and the adsorption of contaminants may easily occur. If the etching treatment is excessive, more zirconia pigment particles are exposed on the surface of the glaze, but zirconia has a low reactivity with hydrophilic compounds, so the hydrophilic performance may decrease. On the other hand, when the etching occurs only on a narrow surface, contaminants adsorbed on the surface cannot be removed, and a hydroxyl group (-OH group) is activated on the surface, thereby increasing the bonding area of the hydrophilic compound does not occur.

However, the lower limit may be 10%, 13%, 16%, 19%, 22%, 25%, 28% or 31%, and the upper limit may be 50%, 47%, 44%, 41%, 38%, 35% or 32%. Through appropriate exposure within this range, excellent antifouling performance and abrasion resistance can be realized, and deterioration of surface roughness and gloss can be prevented.

The etching (treatment) solution is not particularly limited, but for example, 0.01 to 0.4 parts by weight of sulfamic acid, 0.01 to 0.5 parts by weight of ammonium fluoride, and 0.05 to 2 parts by weight of ammonium sulfate based on 100 parts by weight of the etchant in total. and the remainder may be a solvent (water).

Specifically, based on 100 parts by weight of the total etchant, 0.05 to 0.3 parts by weight of sulfamic acid, 0.07 to 0.21 parts by weight of ammonium fluoride, and 0.2 to 1 parts by weight of ammonium sulfate may be included, and the remainder may be a solvent (water).

More specifically, based on 100 parts by weight of the total etchant, sulfamic acid may be included in an amount of more than 0.05 parts by weight and not more than 0.3 parts by weight, more than 0.07 parts by weight of ammonium fluoride and not more than 0.21 parts by weight, and more than 0.2 parts by weight of ammonium sulfate and not more than 1 part by weight. and the remainder may be a solvent (water).

In another exemplary embodiment, 0.1 parts by weight to 0.3 parts by weight of sulfamic acid, 0.1 parts by weight to 0.4 parts by weight of ammonium fluoride, 0.3 parts by weight to 1.5 parts by weight of ammonium sulfate based on 100 parts by weight of the total etchant. and the remainder may be a solvent (water).

When the above content is not satisfied, for example, when the concentration of the etchant is too large, irregularities are excessively generated on the glaze surface of the sanitary ware, thereby reducing the gloss of the product, and on the contrary, adsorption of contaminants may easily occur. On the other hand, when the concentration is too low, as the present application intends, the hydroxyl functional group (-OH group) is not activated on the surface, so that the hydrophilic compound is not easily bound to the surface, so there is a problem in that abrasion resistance and antifouling properties are lowered.

In addition, the etching may be performed for 1 second to 40 seconds or 1 second to 35 seconds. Specifically, it may be performed for 5 seconds to 35 seconds, and may be performed for 10 seconds to 30 seconds. By performing the etching in this range, it is possible to control the zirconium particles of an appropriate height to protrude. The etching time may be appropriately adjusted according to the content of the components included in the etching solution.

By controlling the dilution concentration and treatment time of the etching agent, an appropriate level of etching is generated on the glazed surface of the sanitary ware to remove contaminants, and the surface roughness can be maintained while activating the hydroxyl group.

S30: After applying the coating composition on the surface of the etched pottery, it is cured.

In an exemplary embodiment of the present application, applying the coating composition on the surface of the etched ceramic may mean applying the coating composition on the etched glaze layer.

A coating layer including a hydrophilic compound can be formed by applying a coating composition on the surface of the etched ceramics as described above and curing the coating composition.

The coating composition for forming the coating layer is not particularly limited, but the description of the pottery described above applies mutatis mutandis.

A method of applying the coating composition on the glaze layer is not particularly limited, and may preferably be a spray coating method. In addition, as long as it is a spray method, any device or apparatus used in the art is applicable, not limited thereto, and a coating method used in the art may be appropriately employed.

The curing method is performed using an infrared heating type heat treatment machine within 1 hour at a temperature of 60 °C to 140 °C, preferably within 30 minutes at a temperature of 70 °C to 130 °C.

In an exemplary embodiment of the present application, the method may further include washing the pottery after the curing step.

In an exemplary embodiment of the present application, the step of washing the pottery is performed to remove unreacted hydrophilic compounds, and is performed by spraying water with a spray. However, the washing solution is not limited to water, and any solution capable of washing the coating layer can be applied and used for washing.

In an exemplary embodiment of the present application, after applying the coating composition on the surface of the etched ceramics, the pre-coating composition comprising a silane compound is applied on the surface of the etched ceramics before the curing step. Then, it may further include a step of curing.

That is, when the above step is further included, the pre-coating composition is applied on the surface of the etched pottery and cured to form a pre-coating layer, and then the coating composition including the hydrophilic compound is applied on the pre-coating layer. After curing, a step of forming a coating layer is performed.

The composition for pre-coating forming the pre-coat layer is not particularly limited, but the description of the pottery described above applies mutatis mutandis.

In an exemplary embodiment of the present application, the method of applying the composition for pre-coating on the glaze layer is not particularly limited, and may preferably be a spray method of spray coating. In addition, any device or apparatus used in the art is applicable as long as it is a spray method.

In an exemplary embodiment of the present application, curing of the applied composition for pre-coating is carried out in a drying oven at 80 °C to 140 °C, preferably at 90 °C to 120 °C, more preferably at 110 °C within 1 hour, preferably can be carried out for 30 minutes.

In an exemplary embodiment of the present application, applying a composition for pre-coating on the surface of the etched pottery, and curing the applied composition to form a pre-coat layer, followed by washing the pottery on which the pre-coat layer is formed can do.

In an exemplary embodiment of the present application, the step of washing the pottery on which the pre-coat layer is formed is performed to remove unreacted silane compounds, and ethanol is sprayed to proceed. However, the washing solution is not limited to ethanol, and any solution capable of washing the coating layer may be applied and used for washing.

Hereinafter, an experimental example will be described in detail to describe the present specification in detail. However, the experimental examples according to the present specification may be modified in various other forms, and the scope of the present application is not to be construed as being limited to the experimental examples described in detail below. Experimental examples of the present application are provided to more completely explain the present specification to those of ordinary skill in the art.

[Experimental example]

[Example 1]

Etching was performed for 30 seconds using an etchant containing 0.15 parts by weight of sulfamic acid, 0.21 parts by weight of ammonium fluoride, 0.6 parts by weight of ammonium sulfate, and 99.04 parts by weight of water in the prepared sample sanitary ware.

Then, a pre-coating composition containing a silane compound was applied at 50 g/m ² and cured at 110° C. for 30 minutes to form a pre-coating layer, followed by washing. At this time, the composition for pre-coating included 3-acryloyloxypropyl premethoxysilane, hydrochloric acid, and propylene glycol methyl ether in a weight ratio of 1:1:98, respectively. Then, based on 100 parts by weight, 39.6 parts by weight of sodium 3-allyloxy-2-hydroxy-1-propane sulfonate, 0.99 parts by weight of sodium persulfate, 4.95 parts by weight of urea, 54.44 parts by weight of propylene glycol methyl ether and SDS ( Sodium Dodecyl Sulfate) 0.02 parts by weight of a coating composition was applied on the pre-coating layer at 70 g/m ² and cured at 130° C. for 30 minutes to form a coating layer and washed to prepare a sample of Example 1. .

[Example 2]

The same method as in Example 1, except that etching was performed for 10 seconds using an etchant containing 0.25 parts by weight of sulfamic acid, 0.35 parts by weight of ammonium fluoride, 1 part by weight of ammonium sulfate, and 98.4 parts by weight of water in the prepared sample sanitary ware. to prepare the sample of Example 2.

[Comparative Example 1]

A sample of Comparative Example 1 was prepared in the same manner as in Example 1, except that etching was not performed on the prepared sample sanitary ware.

[Comparative Example 2]

The same method as in Example 1, except that etching was performed for 10 seconds using an etchant containing 0.05 parts by weight of sulfamic acid, 0.07 parts by weight of ammonium fluoride, 0.2 parts by weight of ammonium sulfate and 99.68 parts by weight of water in the prepared sample sanitary ware. to prepare a sample of Comparative Example 2.

[Comparative Example 3]

The same method as in Example 1, except that etching was performed for 1 minute using an etchant containing 0.5 parts by weight of sulfamic acid, 0.7 parts by weight of ammonium fluoride, 2 parts by weight of ammonium sulfate, and 96.8 parts by weight of water in the prepared sample sanitary ware. to prepare a sample of Comparative Example 3.

[Comparative Example 4]

The same method as in Example 1, except that etching was performed for 3 minutes using an etchant containing 0.5 parts by weight of sulfamic acid, 0.7 parts by weight of ammonium fluoride, 2 parts by weight of ammonium sulfate and 96.8 parts by weight of water in the prepared sample sanitary ware to prepare a sample of Comparative Example 4.

[evaluation]

For Examples 1 and 2 and Comparative Examples 1 to 4, physical properties were measured through experiments as follows.

Protrusion height of zirconium particles

The protrusion height of the zirconium particles was measured using Atomic Force Microscopy (AFM). Specifically, the SII Nanocute device of SII NanoTech was used. AR5-NCHR-10 was installed as the cantilever, DFM, non-contact mode was set as the measurement mode, and the microscopic shape of the surface of the sample sanitary ware of size 10×10um ² was measured with an accuracy of 1024/512 pixels/lines. The protrusion height of one zirconium particle is shown in Table 1 below.

Spectral measurement by X-ray photoelectron spectroscopy (XPS)

The analysis results by X-ray photoelectron spectroscopy (XPS) of Examples 1 and 2 and Comparative Examples 1 to 4 are shown as follows.

The spectrum by photoelectron spectroscopy was measured under the following conditions using an X-ray photoelectron spectrometer (manufacturer: Thermo Fisher Scientific, model name: K-Alpha+ X-ray Photoelectron Spectrometer).

Source Type: Al K Alpha

Spot size: 400 um

Analyser mode: pass energy 40 eV

Step size 0.1 eV

Scan number: 15 times

In Examples 1 and 2 and Comparative Examples 1 to 3, a peak appeared at 166 eV to 173 eV, and the element content (atomic%) of S is shown in Table 1 below.

Protrusion height of zirconium particles (nm) Elemental content of S (atomic%) Example 1 37 2.81 Example 2 42 2.78 Comparative Example 1 7 0.53 Comparative Example 2 9 0.61 Comparative Example 3 87 1.76 Comparative Example 4 96 1.56

7 is an AFM image of Example 1, Comparative Example 1, and Comparative Example 3. Specifically, in the case of Example 1, it can be confirmed that the zirconium particles protrude. On the other hand, in the case of Comparative Example 1, it can be seen that the zirconium particles hardly protrude, and in the case of Comparative Example 3, the zirconium particles protrude excessively.

8 is a view showing the protrusion height of zirconium particles in a specific area (part indicated by a dotted line) of the AFM image of Example 1.

Referring to Table 1, in the case of Examples 1 and 2 in which the zirconium particles protrude in the range of 10 nm to 50 nm, it was confirmed that the element content of S on the surface was as high as 2 atomic% or more. On the other hand, when the zirconium particles hardly protrude as in Comparative Examples 1 and 2 or excessively protrude as in Comparative Examples 3 and 4, it could be confirmed that the element content of S on the surface was less than 2 atomic%.

60° gloss

In order to measure the gloss, the 60° gloss of Examples 1 and 2 and Comparative Examples 1 to 4 was measured according to ISO 4281, and is shown in Table 1 below.

contact angle

In order to confirm the hydrophilicity, the contact angles with respect to water of Examples 1 and 2 and Comparative Examples 1 to 4 were measured and shown in Table 1 below.

The contact angle was measured using KRUSS's mobile surface analyzer equipment. The contact angle with water was measured 5 times for 2 seconds after dropping 2 μl of the water droplet and displayed as an average, and the other two locations in the sample were additionally measured and the total average was measured.

surface color

The colors (staining degree) of the surfaces of Examples 1 and 2 and Comparative Examples 1 to 4 were visually observed, and the results are shown in Table 1 below.

self-cleanliness

In order to confirm the self-cleaning property, an experiment was performed by applying oil-based magic to the surface of the specimen for Examples 1 and 2 and Comparative Examples 1 to 4, drying at room temperature for 30 seconds, and then spraying water. It was evaluated as follows and shown in Table 1 below.

5: Most of the ink of oily magic floats (80 to 100%)

4: More than half of the ink of oily magic rises (60 to 80%)

3: Ink of oily magic rises half (40 to 60%)

2: More than half of the oily magic ink does not rise (20-40%)

1: Most of the ink of oily magic does not float (0 to 20%)

easy clean castle

In order to confirm the easy-clean property, an experiment was performed by applying oil-based magic to the surfaces of Examples 1 and 2 and Comparative Examples 1 to 4, drying at room temperature for 30 seconds, spraying water, and rubbing the magic with an experimental wipe-all. It was evaluated as follows and shown in Table 1 below.

5: Almost completely removed by rubbing (80-100%)

4: More than half erased by rubbing (60 to 80%)

3: Half erased by rubbing (40 to 60%)

2: Slightly erased by rubbing (20-40%)

1: No rubbing (0 to 20%)

wear resistance

In order to measure the abrasion resistance, the friction condition is that the product specimen is immersed in water, and the surface of the product is reciprocated and rubbed with a PP (polypropylene) material size 30x40mm bathroom cleaning brush under the condition of 500g load and 100mm friction width.

The antifouling performance of the specimen rubbed 10,000 times under the above conditions was evaluated in the same way as the self-cleaning property, which is to determine whether the antifouling performance immediately after coating is well maintained even after 10,000 wears.

In addition, SEM images for Comparative Example 1, Example 1, and Comparative Example 3 are shown in FIGS. 3 (50 times) and 4 (200 times), respectively. In addition, the SEM image of Example 1 and Comparative Example 1 and the image obtained by measuring the surface roughness are shown in FIG. 5 . In addition, the EDS mapping result image of Example 2 is shown in FIG. 6 .

60° gloss Roughness (㎛) colour Contact angle (°) self-cleaning easy clean wear resistance Example 1 95 0.55 Good 8.5 5 5 5 Example 2 94 0.49 Good 8.7 5 5 4 Comparative Example 1 96 0.49 Good 35.1 One One One Comparative Example 2 93 0.51 Good 31.3 4 3 One Comparative Example 3 86 0.91 spotting 9.1 2 One - Comparative Example 4 81 1.10 spotting 9.4 3 One -

3 and 4, unlike Comparative Example 1, in Example 1, the surface of the glaze was etched, and it was confirmed that fine irregularities were generated when referring to the dark gray area. On the other hand, it was confirmed that Comparative Example 3 was excessively etched.

As shown in FIG. 5 , it was confirmed that, unlike Comparative Example 1, in Example 1, the particle component was further exposed to the surface of the glaze treated with an etching agent, and a fine concavo-convex structure was formed. In addition, most of the zirconium particles are covered with a glaze layer to form a flat surface. The glaze surface of the silica component with relatively low chemical resistance is etched by the etching agent, and the zirconium particles with high chemical resistance are exposed to the surface to form a fine concavo-convex structure. formation could be confirmed.

As shown in FIG. 6 , as a result of the analysis of the glaze surface component of Example 2, the area darkly observed in the SEM image had a lot of silica component, and a small amount of potassium, calcium, and aluminum components were distributed, and the area with a lot of silica component in the glassy glaze layer was etched more, and it was confirmed that fine surface irregularities were generated.

In addition, as shown in Table 2, when the superhydrophilic coating layer was formed after extruding the zirconium particles through an appropriate etching pretreatment as in Examples 1 and 2, appropriate glossiness and roughness could be secured, and the contact angle to water was It was confirmed that it was possible to provide super-hydrophilic properties by controlling it to be less than 10 °. Accordingly, it was confirmed that Examples 1 and 2 had excellent self-cleaning properties and easy-clean properties, so that the contaminant did not adhere well, the attached contaminant was easily removed, and the abrasion resistance was excellent.

On the other hand, when the etch pretreatment process is not performed as in Comparative Example 1, or the zirconium particles do not sufficiently protrude because the pretreatment process is not sufficiently performed with a low concentration etchant as in Comparative Example 2, the superhydrophilic coating is applied to water. It was confirmed that the contact angle with respect to the contact angle exceeded 30° and did not exhibit superhydrophilicity, and for this reason, the self-cleaning and easy-clean properties were poor compared to Examples 1 and 2, and the abrasion resistance was also poor.

As in Comparative Examples 3 and 4, when the zirconium particles were excessively protruded due to excessive etching for a long time with a high-concentration etchant, staining occurred, and the self-cleaning and easy-cleaning properties were also poor compared to Examples 1 and 2. In addition, in Comparative Examples 3 and 4, the antifouling performance immediately after the superhydrophilic coating was poor, and thus the abrasion resistance could not be evaluated.

Although the above has been described with reference to preferred embodiments of the present application, those skilled in the art can variously modify and change the present application without departing from the spirit and scope of the present invention as set forth in the claims below. You will understand that you can.

1: Pottery
11: glaze
13: zirconium particles

Claims (14)

A pottery comprising a glaze layer containing zirconium particles,
The surface of the pottery includes a region in which the zirconium particles protrude from 10 nm to 50 nm with respect to the surface of the glaze layer,
A pottery having a peak present at 158 eV to 175 eV when the surface of the pottery is analyzed by X-ray photoelectron spectroscopy (XPS). According to claim 1,
In the case of analysis by the X-ray photoelectron spectroscopy (XPS), the detected element content (atomic%) of S is 2 atomic% to 4.5 atomic% based on all elements. According to claim 1,
The surface of the pottery will include a region in which the zirconium particles protrude from 15 nm to 45 nm with respect to the surface of the glaze layer. According to claim 1,
The average particle diameter of the zirconium particles protruding from the surface of the glaze layer is 0.1 μm to 2 μm pottery. According to claim 1,
The surface roughness of the pottery will be 0.1 μm to 0.6 μm. According to claim 1,
The pottery wherein the contact angle of the surface of the pottery with respect to water is 15° or less. According to claim 1,
Pottery comprising a coating layer comprising a hydrophilic compound provided on the glaze layer containing the zirconium particles. 8. The method of claim 7,
Pottery further comprising a pre-coating layer containing a silane compound between the glaze layer containing the zirconium particles and the coating layer containing the hydrophilic compound. Preparing a pottery comprising a glaze layer containing zirconium particles;
etching the surface of the pottery with an etchant; and
9. A method of manufacturing a pottery according to any one of claims 1 to 8, comprising the step of applying a coating composition on the etched surface of the pottery and curing the composition. 10. The method of claim 9, further comprising the step of washing the pottery after the curing step. 10. The method of claim 9,
The etchant is a method of producing a pottery comprising 0.01 to 0.4 parts by weight of sulfamic acid, 0.01 to 0.5 parts by weight of ammonium fluoride, and 0.05 to 2 parts by weight of ammonium sulfate based on 100 parts by weight of the total etchant. 10. The method of claim 9,
The coating composition is a method for producing a pottery comprising a hydrophilic compound. 10. The method of claim 9,
After applying the composition for coating on the surface of the etched ceramics, before the curing step, applying a pre-coating composition comprising a silane compound on the surface of the etched ceramics, further comprising the step of curing A method for manufacturing pottery. 10. The method of claim 9,
The etching is a method of manufacturing a pottery that is performed for 1 second to 35 seconds.

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