WO2014193192A1 - Porous ceramic tile with high strength and high hygroscopic and desiccative properties - Google Patents

Porous ceramic tile with high strength and high hygroscopic and desiccative properties Download PDF

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WO2014193192A1
WO2014193192A1 PCT/KR2014/004860 KR2014004860W WO2014193192A1 WO 2014193192 A1 WO2014193192 A1 WO 2014193192A1 KR 2014004860 W KR2014004860 W KR 2014004860W WO 2014193192 A1 WO2014193192 A1 WO 2014193192A1
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porous ceramic
ceramic tile
alumina
weight
aluminum
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French (fr)
Korean (ko)
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강봉규
정승문
강길호
임호연
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(주)엘지하우시스
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Priority to JP2016516456A priority Critical patent/JP6342996B2/en
Priority to CN201480031256.7A priority patent/CN105246854A/en
Publication of WO2014193192A1 publication Critical patent/WO2014193192A1/en

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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
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    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/04—Clay; Kaolin
    • C—CHEMISTRY; METALLURGY
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    • C04B33/00—Clay-wares
    • C04B33/36—Reinforced clay-wares
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0038—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by superficial sintering or bonding of particulate matter
    • C04B38/0041—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by superficial sintering or bonding of particulate matter the particulate matter having preselected particle sizes
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/322—Transition aluminas, e.g. delta or gamma aluminas
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • a porous ceramic tile having high strength and high moisture absorption and moisture resistance having high strength and high moisture absorption and moisture resistance.
  • the thickest tile product of the interior finish is ideal.
  • One embodiment of the present invention provides a porous ceramic tile including a glassy binding material to increase the strength through the role of ⁇ -alumina and a binder having excellent moisture absorption and moisture proof function.
  • a porous ceramic tile comprising from about 15% to about 60% by weight of ⁇ -alumina and from about 5% to about 20% by weight glassy binder.
  • the ⁇ -alumina is a material having a phase change of one aluminum source selected from the group consisting of aluminum nitride, aluminum carbonate, aluminum chloride, aluminum chloride dihydrate, aluminum hydroxide, aluminum chloride, aluminum nitrate, alumina sol, and combinations thereof It may include.
  • the glassy binder may comprise glass frit.
  • the porous ceramic tile may include about 25% to about 65% by weight of the parent material in a total of 100% by weight.
  • the parent material may include one or more selected from the group consisting of clay, clay, loess and combinations thereof.
  • It may further comprise one or more additives selected from the group consisting of diatomaceous earth, feldspar, pottery, lime, milky and combinations thereof.
  • the porous ceramic tile may include about 5 wt% or less of the additive based on 100 wt% of the total.
  • the bending strength of the porous ceramic tile may be about 10 MPa to about 20 MPa.
  • Moisture absorption and moisture absorption of the porous ceramic tile may be about 60g / m 2 to about 100g / m 2 .
  • the porous ceramic tile may include porous ceramic tile forming particles connected by the glassy binder.
  • the porosity of the porous ceramic tile forming particles may be about 30% to about 50%.
  • the porous ceramic tile may include pores having an average diameter of about 0.5 ⁇ m to about 50 ⁇ m.
  • the porous ceramic tile may be used as a functional tile by maintaining and enhancing moisture absorption and at the same time promoting low plastic strength.
  • FIG. 1 is a schematic view showing a porous ceramic tile of an embodiment of the present invention.
  • FIG. 2 is a schematic view showing a conventional porous ceramic tile.
  • a porous ceramic tile comprising 15 wt% to 60 wt% of ⁇ -alumina and 5 wt% to 20 wt% of the glassy binder.
  • porous ceramic tiles require a calcination process, and the tiles may be classified according to the firing temperature range. It is generally classified into polishing tiles formed by firing at a temperature above about 1300 ° C, magnetic tiles formed by firing at a temperature below about 1300 ° C, and ceramic tiles formed by firing at a temperature of about 800 ° C. The denser the tissue, the higher the bending strength.
  • the firing process is performed at about 1000 ° C or less to make open pores for smooth entry and exit of air, and as a result, the structure is less dense and stronger than general porcelain and polishing tiles. There was a weak problem.
  • the content ratio of the ⁇ -alumina and the glassy binding material serving as a binder in the porous ceramic tile composition was controlled.
  • the ceramic tile may comprise about 15% to about 60% by weight ⁇ -alumina and about 5% to about 20% by weight glassy binder.
  • the ⁇ -alumina can impart a humidity control function as alumina in a transition state.
  • heat treatment of aluminum source it can be transformed into other structures, and has a large specific surface area and fine pore holes, and thus can exhibit excellent properties as a separator, catalyst, catalyst carrier and adsorbent.
  • the ⁇ -alumina may be formed on the surface of the pores of the porous ceramic tile-forming particles may have excellent humidity and deodorization function. Accordingly, the ⁇ -alumina absorbs moisture through the pores when the humidity is high to lower the humidity in the room, and conversely, when the humidity is low, the ⁇ -alumina releases moisture stored in the pores to increase the indoor humidity. do.
  • the commercially available ⁇ -alumina may be used as the ⁇ -alumina, specifically, a ⁇ -alumina obtained by phase-transferring an inexpensive aluminum source by heat treatment may be used in view of cost reduction and efficiency.
  • the ⁇ -alumina may comprise about 15% to about 60% by weight, specifically about 10% to about 35% by weight. When the ⁇ -alumina is less than about 15% by weight, it may be difficult to exhibit a sufficient humidity control function. When the ⁇ -alumina is less than about 60% by weight, the strength of the tile may be lowered as the sinterability of the porous ceramic tile is lowered. have.
  • ⁇ -alumina in the above range, it is possible to exert a high humidity control function and to secure a stable tile strength.
  • the specific surface area of the ⁇ -alumina is not particularly limited, but may be, for example, about 150 m 2 / g to about 350 m 2 / g.
  • the specific surface area of the ⁇ -alumina is less than about 150 m 2 / g, sufficient humidity control function may not be exhibited, and when it exceeds about 350 m 2 / g, it may cause difficulty in the manufacturing process and may increase the manufacturing cost. have.
  • the ⁇ -alumina has a top surface of one aluminum source selected from the group consisting of aluminum nitride, aluminum carbonate, aluminum chloride, aluminum chloride dihydrate, aluminum hydroxide, aluminum chloride, aluminum nitrate, alumina sol, and combinations thereof. It may comprise a substance.
  • the alumina source is not limited to the examples, and any aluminum source that may be phase-shifted into ⁇ -alumina by heat treatment may be included therein.
  • the ⁇ -alumina conversion of aluminum hydroxide may be about 0.6 to about 0.7.
  • the porous ceramic tile may comprise a glassy binder.
  • the glassy binder refers to a glassy material containing about 75% or more of glass.
  • the glassy material refers to an amorphous solid state without crystallization and long distance regularity in the arrangement of atoms when rapidly cooled in a molten state.
  • the glassy binder may include about 5% by weight to about 20% by weight. If the glassy binder is less than about 5% by weight, there is a concern that the plastic strength is weakened, and when the glassy binder material exceeds about 20% by weight, the manufacturing cost is increased. Therefore, it is possible to easily implement the effect of exhibiting a high plastic strength compared to the manufacturing cost by including the glassy binder material in the content range.
  • the glassy binder may comprise glass frit.
  • the glass frit is a low melting point glass that starts to melt at a temperature of about 700 ° C. lower than the firing temperature of a general tile to facilitate movement between particles in the tile firing process, and increases the strength of the porous ceramic tile by acting as an adhesive, that is, a binder. Play a role.
  • the glass frit due to the role of the binder, reduces the pores that are the entrance and exit passages of air between the porous ceramic tile forming particles and prevents pores exhibiting moisture absorptive and moisture absorptive properties on the surface of the porous ceramic tile forming particles by ⁇ -alumina. can do.
  • the pores between the porous ceramic tile forming particles are reduced by the glassy binding material, and the lowering of moisture absorption and moisture absorption can be suppressed due to the blocking of pores on the surface of the porous ceramic tile forming particles. .
  • the porous ceramic tile may include a parent material in addition to the ⁇ -alumina and the glassy binder.
  • the parent material is a material that serves as a base material constituting the porous ceramic tile, that is, a material serving as a skeleton in the tile, specifically, the parent material is one or more selected from the group consisting of clay, clay, loess, and combinations thereof It may include.
  • the content of the parent material is not particularly limited, and the content of the parent material may vary as other additives are added according to the application and use of the porous ceramic tile. 25 weight percent to about 65 weight percent. By including the parent material in the above range can be imparted appropriate moldability and sinterability to the porous ceramic tile, it is possible to ensure the mechanical stability.
  • the porous ceramic tile may further include one or more additives selected from the group consisting of diatomaceous earth, feldspar, pottery, lime, milky, and combinations thereof.
  • the content of the additive is not particularly limited, and may be appropriately employed within a range in which the function of the porous ceramic tile is not impaired.
  • the porous ceramic tile may include about 5% by weight or less of the additive, specifically about 3% by weight or less, based on 100% by weight.
  • the content of the additive the content of ⁇ -alumina, glassy binder and parent material can be adjusted appropriately, so that the function of physical stability and moisture absorption and moisture resistance of the porous ceramic tile such as molding strength and plastic strength can be maintained at a certain level. have.
  • Diatomaceous earth in the additive is a porous, rich in water absorption, when added to the porous ceramic tile formation can further improve the hygroscopic function, and other silica, feldspar, stone and lime can also be included in the appropriate amount.
  • the whitening agent is a powder added to give a white color to the glass product, the type is not particularly limited, but at least one selected from the group consisting of chloride, tin, titanium oxide, sulfate, phosphate, arsenate and fluoride It may include.
  • the bending strength of the porous ceramic tile may be about 10 MPa to about 20 MPa. Bending strength refers to the maximum tensile stress at break in bending test, which means the maximum tensile stress at break of porous ceramic tile when bending pressure is applied to the porous ceramic tile.
  • the bending strength of a conventional porous ceramic tile is measured to have a bending strength of less than about 10 Mpa, but the porous ceramic tile includes about 5% by weight to about 20% by weight of glassy binder, which acts as a binder, thereby providing a general porous ceramic. It can secure the bending strength improved by about 100% more than the bending strength of the tile.
  • the bending strength of general ceramic tiles other than porous ceramics is about 20MPa. In this case, breakage occurs rarely during transportation and construction. Therefore, the bending strength of the porous ceramic tile is similar to the bending strength of the general ceramic tile, thereby minimizing damage, crack production, etc. due to physical shocks generated during the production, transportation, and construction of the porous ceramic tile, and reducing the loss rate. Can reduce the production cost and improve the construction speed.
  • Moisture absorption and moisture absorption of the porous ceramic tile may be about 60g / m 2 to about 100g / m 2 .
  • Moisture absorption and moisture absorption of the porous ceramic tile is necessary to control the humidity in the medium-humidity region (temperature about 25 °C, relative humidity about 50% to about 75%) that humans can live the most comfortable life, the moisture absorption amount of the tile Can be calculated as the average of the amount of moisture and moisture.
  • the porous ceramic tile may include about 15 wt% to about 60 wt% of ⁇ -alumina, and may include pores having a predetermined porosity or more on the surface of the porous ceramic tile forming particle.
  • the content of the ⁇ -alumina and at the same time to control the content of the glassy binder material, between the porous ceramic tile-forming particles of a certain size to facilitate the entry and exit of air Pore can be secured.
  • the porous ceramic tile may include porous ceramic tile forming particles connected by the glassy binder.
  • the porous ceramic tile forming particles may be connected by a glassy binder material, and may include micropores on the surface of the porous ceramic tile forming particles and open pores between the porous ceramic tile forming particles.
  • the porous ceramic tile-forming particles may include micropores blocked at the same time as the micropore and the glassy binding material, it is possible to optimize the bending strength and moisture absorption by adjusting the content of each material.
  • the porous ceramic tile is compared with FIG. 2 shown in a schematic diagram of a conventional porous ceramic tile, by controlling the content of the ⁇ -alumina and the glassy binder forming the porous ceramic tile, the glassy binder further serves as a binder By strengthening, it is possible to secure a higher strength than conventional porous ceramic tiles.
  • the porosity of the porous ceramic tile forming particles may be about 30% to about 50%.
  • the porosity of the open pores formed between the micropores distributed on the surface of the porous ceramic tile forming particles and the porous ceramic tile forming particles is a numerical value representing the degree of the pores of the micropores and open pores, that is, The porosity refers to the percentage of open pore and micropore volume inside the tile to the total volume of the porous tile forming particles.
  • the porous ceramic tile includes a glassy binder in addition to ⁇ -alumina, micropores may be blocked by the glassy binder, but by controlling the content of the ⁇ -alumina and the glassy binder, the porosity in the range may be adjusted. It is possible to maintain, and thus it is possible to easily implement the excellent humidity control effect due to the high humidity control function.
  • the porous ceramic tile may include pores having an average diameter of about 0.5 ⁇ m to about 50 ⁇ m.
  • the upper pores are pores formed between the porous ceramic tile-forming particles, also called open pores, and mean spaces for smoothly entering and exiting air. More specifically, the mean diameter of the pores refers to an arithmetic mean value of the open pore diameters.
  • the porous ceramic tile serves as a binder or an adhesive by including a glassy binder material
  • the porous ceramic tile has a smaller average diameter of open pores, compared to the open pores of a conventional porous ceramic tile, but the content of the glassy binder material is increased. It is possible to maintain the average diameter of the open pores within the above range, thereby ensuring a smooth flow for entering and entering the air and moisture, and the strength of the tile is maintained high ⁇ - having fine pores inside the tile
  • the relative amount of alumina is kept constant to ensure the humidity control function.
  • the porous ceramic tile may include pores having an average diameter of about 1 nm to about 50 nm.
  • the pores may be micropores distributed on the surface of the porous ceramic tile-forming particles, the micropores can maintain a high strength of the tile by maintaining the average diameter of the range, it is also possible to ensure the humidity control function.
  • the porous ceramic tile includes both the glassy binder and the ⁇ -alumina at the same time, thereby ensuring both strength and moisture absorption and moisture absorption of the porous ceramic tile.
  • the mixture of the solid components shown in Table 1 is pulverized through a ball mill by adding about 20-50% of water to the total amount (%), and the slurry thus obtained is uniformly mixed through a spray drying process and the water content is 8%, average A spherical granular powder having a particle size of 300 ⁇ m was prepared. At this time, the prepared granulated powder includes the solid components shown in Table 2 below.
  • the granular powder was dry press-molded to prepare porous ceramic tiles having a width, length, and thickness of 5 cm, 5 cm, and 0.6 cm, respectively. Next, it was put in an electric furnace (Furnace) and baked for 5 minutes at a temperature of 850 °C to prepare a porous ceramic tile.
  • aluminum hydroxide (Al (OH) 3 ) is converted into ⁇ -alumina (Al 2 O 3) and calcined coal (CaCO 3) into quicklime (CaO) during the manufacturing process, and the ⁇ -alumina conversion of aluminum hydroxide is about 0.6 to about. 0.7, and the quicklime conversion of the coal can be about 0.5 to about 0.6.
  • the ⁇ -alumina conversion of aluminum hydroxide is 0.654 and the quicklime conversion of the coal is 0.56.
  • Example 1 clay Aluminum hydroxide Glass frit burr Sancheong soil Charcoal Pigment Sum Example 1 46.2 19.6 11 1.5 2.2 17.7 0.8 100
  • Example 2 39.6 29.3 11 1.3 1.9 15.2 0.7 100
  • Example 3 37.6 29.3 14 1.2 1.8 14.4 0.7 100
  • Example 4 31 39.1 14 One 1.5 11.9 0.5 100
  • Example 5 35.5 29.3 15.5 1.1 1.7 13.6
  • Example 6 28.9 39.1 15.5 0.9 1.4 11.1 0.6 100
  • Comparative Example 1 56 10 17.5 0.9 1.4 11.1 0.6 100
  • Comparative Example 2 16 70 5 0.9 1.4 11.1 0.6 100 Comparative Example 3 33 50 3 0.9 1.4 11.1 0.6 100 Comparative Example 4 41 20 25 0.9 1.4 11.1 0.6 100
  • the bending strength is calculated by (3PL) / (2wt ⁇ 2), where P is the maximum load when the tile is broken, L is the outer gap, w is the width of the tile, and t is the thickness of the tile.
  • Examples 1 to 6 are porous tiles formed of 15 wt% to 60 wt% of ⁇ -alumina and 5 wt% to 20 wt% of glass frit, and about 10 MPa for flexural strength.
  • the basis weight which is measured in the range of about 20 MPa and exhibits moisture absorption and moisture absorption, was about 60 g / m 2 or more.
  • the porous ceramic tile secures flexural strength and moisture absorption at the same time according to the content control of the glassy binder and ⁇ -alumina. Inference could be inferred.
  • Comparative Example 1 containing less than ⁇ -alumina, the flexural strength was optimized, but glass frit did not secure moisture absorption by blocking pores of the porous tile, and compared with ⁇ -alumina content.
  • Comparative Example 2 which contains a large amount, the content of the parent material, i.e., the clay, was relatively low, so that the plastic (molding) strength was reduced, which was destroyed during firing in the manufacture of the porous ceramic tile.
  • Comparative Example 3 containing less than the glassy binder content, the moisture absorption and moisture absorption was optimized due to the content of ⁇ -alumina, but had a weak strength due to the content of the low glassy binder material, In the case of Comparative Example 4 containing a lot compared to the fracture due to the excessive shrinkage during firing due to the excessive glassy binder material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
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  • Porous Artificial Stone Or Porous Ceramic Products (AREA)

Abstract

Disclosed is a porous ceramic tile including 15% to 60% by weight of γ-alumina and 5% to 20% by weight of a glassy chain material.

Description

고강도 및 고흡방습성을 갖는 다공성 세라믹 타일Porous ceramic tile with high strength and moisture absorption
고강도 및 고흡방습성을 갖는 다공성 세라믹 타일에 관한 것이다. A porous ceramic tile having high strength and high moisture absorption and moisture resistance.
최근 건축물의 초고층화, 고단열 및 고기밀화로 인해 실내공기를 외부 공기와 강제로 환기시키지 않는 이상 실내 공기의 질은 저하될 수밖에 없는 실정이다. 특히, 여름철 높은 실내습도로 인해 거실 창이나 실내의 구석진벽에 결로가 발생하고, 그로 인해 곰팡이, 진드기 등이 발생하여 호흡기 질환 및 아토피 등의 발생을 유발하는 문제가 발생하고 있다.   In recent years, the quality of indoor air is deteriorated unless the indoor air is forcedly ventilated with the outside air due to the ultra high rise, high insulation, and high density of buildings. In particular, condensation occurs in the living room window or in the corner walls of the room due to high indoor humidity in summer, thereby causing mold, mites, and the like, causing problems such as respiratory diseases and atopy.
이러한 문제를 해결하고자, 습도가 높을 때에는 습기를 빨아들여서 실내 습도를 낮추었다가 건조해지면 흡수한 수분을 내보내서 습도를 높여줄 수 있는 습도조절기능을 가지는 실내 마감용 건축자재의 개발이 필요한 실정이다. In order to solve this problem, it is necessary to develop a building material for interior finishing having a humidity control function that can absorb moisture when the humidity is high and lower the indoor humidity and then, when it is dried, absorb the moisture to increase the humidity.
상기 습도조절기능을 최대화하기 위해서는 조습기능을 발휘하는 제올라이트, 규조토 등의 핵심물질을 최대한 많이 담지 할 수 있어야 하는바, 일반적으로, 실내 마감재 중 두께가 가장 두꺼운 타일 제품이 이상적이다. In order to maximize the humidity control function should be able to support as much as possible the core material, such as zeolite, diatomaceous earth exhibiting a humidity control function, in general, the thickest tile product of the interior finish is ideal.
하지만, 현재까지 국내에서 기능성 타일로 출시되는 제품들은 전반적으로 흡습,방습 기능은 있지만 타일의 강도 등 물리적 성질이 떨어진다는 단점이 있으며, 기능성보다는 디자인을 우선시하여 제조한 것들이 대부분이어서 흡방습기능을 확보함과 동시에 강도 및 물리적 특성을 발휘하는 세라믹 성형체에 대한 기술 개발이 필요한 실정이다.However, until now, products that are released in Korea as functional tiles generally have moisture absorption and moistureproof functions, but the physical properties such as the strength of the tiles are inferior, and most of them are manufactured with priority on design rather than functionality, thus ensuring moisture absorption and moisture absorption. At the same time, there is a need for technology development for ceramic moldings that exhibit strength and physical properties.
본 발명의 일 구현예는 흡습 및 방습 기능이 우수한 γ-알루미나 및 바인더 역할을 통해 강도를 높여주는 유리질 결합물질을 포함하는 다공성 세라믹 타일을 제공한다.One embodiment of the present invention provides a porous ceramic tile including a glassy binding material to increase the strength through the role of γ-alumina and a binder having excellent moisture absorption and moisture proof function.
본 발명의 일 구현예에서, γ-알루미나 약 15중량% 내지 약 60중량% 및 유리질 결합물질 약 5중량% 내지 약 20중량%를 포함하는 다공성 세라믹 타일을 제공한다.In one embodiment of the invention, there is provided a porous ceramic tile comprising from about 15% to about 60% by weight of γ-alumina and from about 5% to about 20% by weight glassy binder.
상기 γ-알루미나는 질화알루미늄, 탄산알루미늄, 염화알루미늄, 염화알루미늄 이수화물, 수산화알루미늄, 알루미늄클로라이드, 알루미늄 나이트래이트, 알루미나 졸 및 이들의 조합으로 이루어진 군으로부터 선택된 하나의 알루미늄 소스가 상변이된 물질을 포함할 수 있다. The γ-alumina is a material having a phase change of one aluminum source selected from the group consisting of aluminum nitride, aluminum carbonate, aluminum chloride, aluminum chloride dihydrate, aluminum hydroxide, aluminum chloride, aluminum nitrate, alumina sol, and combinations thereof It may include.
상기 유리질 결합물질은 유리 프리트를 포함할 수 있다. The glassy binder may comprise glass frit.
상기 다공성 세라믹 타일은 총 100중량% 중 모물질을 약 25중량% 내지 약 65중량%를 포함할 수 있다. The porous ceramic tile may include about 25% to about 65% by weight of the parent material in a total of 100% by weight.
상기 모물질은 점토, 백토, 황토 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상을 포함할 수 있다. The parent material may include one or more selected from the group consisting of clay, clay, loess and combinations thereof.
규조토, 장석, 도석, 석회, 유백제 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상의 첨가물을 추가로 포함할 수 있다. It may further comprise one or more additives selected from the group consisting of diatomaceous earth, feldspar, pottery, lime, milky and combinations thereof.
상기 다공성 세라믹 타일은 총 100중량%에 대해서 상기 첨가물을 약 5중량%이하 포함할 수 있다. The porous ceramic tile may include about 5 wt% or less of the additive based on 100 wt% of the total.
상기 다공성 세라믹 타일의 굽힘강도는 약 10MPa 내지 약 20MPa일 수 있다. The bending strength of the porous ceramic tile may be about 10 MPa to about 20 MPa.
상기 다공성 세라믹 타일의 흡방습량이 약 60g/m2 내지 약 100g/m2일 수 있다.Moisture absorption and moisture absorption of the porous ceramic tile may be about 60g / m 2 to about 100g / m 2 .
상기 다공성 세라믹 타일은 상기 유리질 결합물질에 의해 연결된 다공성 세라믹 타일 형성입자를 포함할 수 있다. The porous ceramic tile may include porous ceramic tile forming particles connected by the glassy binder.
상기 다공성 세라믹 타일 형성입자의 기공률이 약 30% 내지 약 50%일 수 있다. The porosity of the porous ceramic tile forming particles may be about 30% to about 50%.
상기 다공성 세라믹 타일은 평균 직경이 약 0.5㎛ 내지 약 50㎛인 기공을 포함할 수 있다. The porous ceramic tile may include pores having an average diameter of about 0.5 μm to about 50 μm.
상기 다공성 세라믹 타일은 흡방습성을 유지 및 증진시키며 동시에 낮은 소성강도를 증진시켜 기능성 타일로 사용될 수 있다. The porous ceramic tile may be used as a functional tile by maintaining and enhancing moisture absorption and at the same time promoting low plastic strength.
도 1은 본 발명의 일실시예인 다공성 세라믹 타일을 도식화 하여 나타낸 것이다.1 is a schematic view showing a porous ceramic tile of an embodiment of the present invention.
도 2는 종래의 다공성 세라믹 타일을 도식화 하여 나타낸 것이다.2 is a schematic view showing a conventional porous ceramic tile.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구항의 범주에 의해 정의될 뿐이다. Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.
본 발명의 일 구현예에서, γ-알루미나 15중량% 내지 60중량% 및 유리질 결합물질 5중량% 내지 20중량%를 포함하는 다공성 세라믹 타일을 제공한다. In one embodiment of the present invention, there is provided a porous ceramic tile comprising 15 wt% to 60 wt% of γ-alumina and 5 wt% to 20 wt% of the glassy binder.
통상의 다공성 세라믹 타일은 제작하는데 있어서 소성과정이 필요한데 소성온도 영역에 따라 타일을 분류할 수 있다. 보통 약 1300℃이상의 온도에서 소성되어 형성되는 폴리싱 타일, 약 1300℃미만의 온도에서 소성되어 형성되는 자기질 타일, 그리고 약 800℃의 온도에서 소성되어 형성되는 도기질 타일로 분류되는데 상기 소성온도가 높을수록 조직이 치밀하며 높은 굽힘 강도를 나타낸 것이 일반적이다. In general, porous ceramic tiles require a calcination process, and the tiles may be classified according to the firing temperature range. It is generally classified into polishing tiles formed by firing at a temperature above about 1300 ° C, magnetic tiles formed by firing at a temperature below about 1300 ° C, and ceramic tiles formed by firing at a temperature of about 800 ° C. The denser the tissue, the higher the bending strength.
종래의 다공성 세라믹 타일은 당사는 공기의 입·출입을 원활하게 하기 위한 열린기공을 만들기 위하여 소성과정이 약 1000℃이하에서 이루어졌고, 이로 인해 일반 자기 및 폴리싱 타일에 비하여 조직이 치밀하지 못하고 강도가 약한 문제적이 있었다. In the conventional porous ceramic tiles, the firing process is performed at about 1000 ° C or less to make open pores for smooth entry and exit of air, and as a result, the structure is less dense and stronger than general porcelain and polishing tiles. There was a weak problem.
따라서, 이를 보완하기 위해 바인더 역할을 할 수 있는 유리질 물질을 일정량 첨가시켰으나, 유리질 물질의 함량을 증가할수록 공기가 드나드는 기공을 막고, 조습기능을 발휘하는 핵심물질의 미세기공을 막아 흡방습성이 저하될 우려가 있었다. Therefore, to compensate for this, a certain amount of glass material that can act as a binder is added, but as the content of the glass material increases, air pores are prevented from entering and air pores are prevented, and micropores of the core material exhibiting humidity control function decrease moisture absorption and moisture absorption. There was a concern.
이에, 본 발명에서는 흡방습성의 저하없이 조습타일의 굽힘 강도를 향상시키기 위하여, 다공성 세라믹 타일 조성물 내에 조습기능을 하는 γ-알루미나 및 바인더 역할을 하는 유리질 결합물질의 함유 비율을 조절하였는바, 상기 다공성 세라믹 타일은 γ-알루미나 약 15중량% 내지 약 60중량% 및 유리질 결합물질 약 5중량% 내지 약 20중량%를 포함할 수 있다. Therefore, in the present invention, in order to improve the bending strength of the humidity control tiles without deteriorating moisture absorption and moisture content, the content ratio of the γ-alumina and the glassy binding material serving as a binder in the porous ceramic tile composition was controlled. The ceramic tile may comprise about 15% to about 60% by weight γ-alumina and about 5% to about 20% by weight glassy binder.
상기 γ-알루미나는 전이상태의 알루미나로써 조습기능을 부여할 수 있다. 알루미늄 소스를 열처리함으로써 다른 구조상으로 변이가 가능하고, 넓은 비표면적과 미세한 기공 홀을 가지고 있어서 분리막, 촉매, 촉매 담체 및 흡착제로서 우수한 특성을 나타낼 수 있는 물질이다. The γ-alumina can impart a humidity control function as alumina in a transition state. By heat treatment of aluminum source, it can be transformed into other structures, and has a large specific surface area and fine pore holes, and thus can exhibit excellent properties as a separator, catalyst, catalyst carrier and adsorbent.
상기 γ-알루미나는 다공성 세라믹 타일 형성 입자가 포함하는 기공 표면에 형성되어 우수한 조습 및 탈취 기능을 가질 수 있다. 이에 따라, 상기 γ-알루미나는 습도가 높을 때에 상기 기공을 통하여 습기를 흡수하여 실내의 습도를 낮추는 기능을 하고, 반대로 습도가 낮을 때에는 상기 기공 내에 저장되어 있던 습기를 방출하여 실내 습도를 높이는 기능을 한다. 또한, 상기 γ-알루미나는 상용 γ-알루미나를 사용할 수도 있으나, 비용절감 및 효율성의 측면에서, 구체적으로는 저가의 알루미늄 소스를 열처리에 의하여 상 변이시킨 γ-알루미나를 사용할 수 있다.The γ-alumina may be formed on the surface of the pores of the porous ceramic tile-forming particles may have excellent humidity and deodorization function. Accordingly, the γ-alumina absorbs moisture through the pores when the humidity is high to lower the humidity in the room, and conversely, when the humidity is low, the γ-alumina releases moisture stored in the pores to increase the indoor humidity. do. In addition, although the commercially available γ-alumina may be used as the γ-alumina, specifically, a γ-alumina obtained by phase-transferring an inexpensive aluminum source by heat treatment may be used in view of cost reduction and efficiency.
상기 γ-알루미나는 약 15중량% 내지 약 60중량%, 구체적으로 약 10중량% 내지 약 35중량%를 포함할 수 있다. 상기 γ-알루미나가 약 15중량% 미만인 경우, 충분한 조습 기능을 나타내기 어려워질 우려가 있으며, 약 60중량%를 초과하는 경우, 다공성 세라믹 타일의 소결성이 저하됨에 따라 타일의 강도가 저하될 우려가 있다.The γ-alumina may comprise about 15% to about 60% by weight, specifically about 10% to about 35% by weight. When the γ-alumina is less than about 15% by weight, it may be difficult to exhibit a sufficient humidity control function. When the γ-alumina is less than about 60% by weight, the strength of the tile may be lowered as the sinterability of the porous ceramic tile is lowered. have.
그러므로 γ-알루미나를 상기 범위만큼 포함함으로써 높은 조습기능을 발휘하고 안정된 타일의 강도를 확보할 수 있다. Therefore, by including γ-alumina in the above range, it is possible to exert a high humidity control function and to secure a stable tile strength.
또한, 상기 γ-알루미나의 비표면적이 특별히 제한되는 것은 아니지만, 예를 들어 약 150㎡/g 내지 약 350㎡/g인 것일 수 있다. 상기 γ-알루미나의 비표면적이 약 150㎡/g 미만인 경우, 충분한 조습기능을 나타낼 수가 없고, 약 350㎡/g를 초과하는 경우, 제조공정의 어려움을 초래할 수 있으며, 제조비용을 상승시킬 우려가 있다.In addition, the specific surface area of the γ-alumina is not particularly limited, but may be, for example, about 150 m 2 / g to about 350 m 2 / g. When the specific surface area of the γ-alumina is less than about 150 m 2 / g, sufficient humidity control function may not be exhibited, and when it exceeds about 350 m 2 / g, it may cause difficulty in the manufacturing process and may increase the manufacturing cost. have.
구체적으로, 상기 γ-알루미나는 질화알루미늄, 탄산알루미늄, 염화알루미늄, 염화알루미늄 이수화물, 수산화알루미늄, 알루미늄클로라이드, 알루미늄 나이트래이트, 알루미나 졸 및 이들의 조합으로 이루어진 군으로부터 선택된 하나의 알루미늄 소스가 상변이된 물질을 포함할 수 있다. 다만, 상기 알루미나 소스가 예시한 것에 한정되는 것은 아니고, 열처리에 의하여 γ-알루미나로 상변이 될 수 있는 모든 알루미늄 소스가 이에 포함될 수 있다. Specifically, the γ-alumina has a top surface of one aluminum source selected from the group consisting of aluminum nitride, aluminum carbonate, aluminum chloride, aluminum chloride dihydrate, aluminum hydroxide, aluminum chloride, aluminum nitrate, alumina sol, and combinations thereof. It may comprise a substance. However, the alumina source is not limited to the examples, and any aluminum source that may be phase-shifted into γ-alumina by heat treatment may be included therein.
예를 들어, 수산화알루미늄(Al(OH)3)이 γ-알루미나(Al2O3)로 상변화하는 경우, 수산화알루미늄의 γ-알루미나 전환율은 약 0.6 내지 약 0.7일 수 있다. For example, when aluminum hydroxide (Al (OH) 3 ) phase changes to γ-alumina (Al 2 O 3), the γ-alumina conversion of aluminum hydroxide may be about 0.6 to about 0.7.
상기 다공성 세라믹 타일은 유리질 결합물질을 포함할 수 있다. 상기 유리질 결합물질이란 약 75%이상의 유리를 함유하는 유리질 물질을 일컫는바, 상기 유리질은 용융상태에서 급속히 냉각하는 경우 결정화하지 않고 원자의 배열에 장거리 규칙도가 없는 무정형 고체상태를 의미한다. The porous ceramic tile may comprise a glassy binder. The glassy binder refers to a glassy material containing about 75% or more of glass. The glassy material refers to an amorphous solid state without crystallization and long distance regularity in the arrangement of atoms when rapidly cooled in a molten state.
구체적으로, 상기 유리질 결합물질은 약 5중량% 내지 약 20중량%를 포함할 수 있다. 상기 유리질 결합물질이 약 5중량% 미만인 경우 소성강도가 약해지는 염려가 있고, 약 20중량%를 초과하는 경우 제작비용이 증가되는 문제점이 있다. 그러므로, 상기 함량범위의 유리질 결합물질을 포함함으로써 제작비용대비 높은 소성강도를 발휘하는 효과를 용이하게 구현할 수 있다.Specifically, the glassy binder may include about 5% by weight to about 20% by weight. If the glassy binder is less than about 5% by weight, there is a concern that the plastic strength is weakened, and when the glassy binder material exceeds about 20% by weight, the manufacturing cost is increased. Therefore, it is possible to easily implement the effect of exhibiting a high plastic strength compared to the manufacturing cost by including the glassy binder material in the content range.
상기 유리질 결합물질은 유리 프리트를 포함할 수 있다. 상기 유리 프리트는 저융점 유리로써 일반적인 타일의 소성온도보다 낮은 약 700℃정도의 온도에서 녹기 시작하여 타일 소성과정에서 입자간에 이동이 용이하게 하며 접착제, 즉 바인더 역할을 하여 다공성 세라믹 타일의 강도를 높이는 역할을 한다. The glassy binder may comprise glass frit. The glass frit is a low melting point glass that starts to melt at a temperature of about 700 ° C. lower than the firing temperature of a general tile to facilitate movement between particles in the tile firing process, and increases the strength of the porous ceramic tile by acting as an adhesive, that is, a binder. Play a role.
상기 유리 프리트는 바인더 역할로 인하여, 다공성 세라믹 타일 형성입자 사이에 공기의 입출입 통로인 기공을 작게하고 γ-알루미나에 의해 다공성 세라믹 타일 형성입자 표면에서 흡방습성을 발휘하는 기공을 막게 되어 흡방습성을 저하할 수 있다. 그러나, 상기 유리질 결합물질의 함량을 조절함으로써, 유리질 결합물질에 의해 다공성 세라믹 타일 형성입자 사이의 기공이 작아지고, 다공성 세라믹 타일 형성 입자 표면의 기공이 막혀 발생하는 흡방습성 저하현상을 억제시킬 수 있다. The glass frit, due to the role of the binder, reduces the pores that are the entrance and exit passages of air between the porous ceramic tile forming particles and prevents pores exhibiting moisture absorptive and moisture absorptive properties on the surface of the porous ceramic tile forming particles by γ-alumina. can do. However, by controlling the content of the glassy binder material, the pores between the porous ceramic tile forming particles are reduced by the glassy binding material, and the lowering of moisture absorption and moisture absorption can be suppressed due to the blocking of pores on the surface of the porous ceramic tile forming particles. .
상기 다공성 세라믹 타일은 상기 γ-알루미나 및 유리질 결합물질 이외에 모물질을 포함할 수 있다. 상기 모물질은 상기 다공성 세라믹 타일을 구성하는 기초 모재가 되는 물질, 즉 타일 내에서 뼈대 역할을 하는 물질로서, 구체적으로 상기 모물질은 점토, 백토, 황토 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상을 포함할 수 있다. The porous ceramic tile may include a parent material in addition to the γ-alumina and the glassy binder. The parent material is a material that serves as a base material constituting the porous ceramic tile, that is, a material serving as a skeleton in the tile, specifically, the parent material is one or more selected from the group consisting of clay, clay, loess, and combinations thereof It may include.
상기 모물질의 함량은 특별히 제한되는 것은 아니고, 다공성 세라믹 타일의 적용분야 및 용도에 따라 기타 다른 첨가물이 첨가됨에 따라 그 함량이 달라질 수 있는 것으로, 예를 들면 총 100중량% 중 상기 모물질을 약 25중량% 내지 약 65중량%를 포함할 수 있다. 상기 범위의 모물질을 포함함으로써 상기 다공성 세라믹 타일에 적절한 성형성 및 소결성을 부여할 수 있고, 나아가 기계적 안정성을 확보할 수 있다.The content of the parent material is not particularly limited, and the content of the parent material may vary as other additives are added according to the application and use of the porous ceramic tile. 25 weight percent to about 65 weight percent. By including the parent material in the above range can be imparted appropriate moldability and sinterability to the porous ceramic tile, it is possible to ensure the mechanical stability.
상기 다공성 세라믹 타일은 규조토, 장석, 도석, 석회, 유백제 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상의 첨가물을 추가로 포함할 수 있다. 상기 첨가물의 함량은 특별히 제한되는 것은 아니고, 상기 다공성 세라믹 타일의 기능이 손상되지 않는 범위 내에서 적절하게 채용할 수 있다.The porous ceramic tile may further include one or more additives selected from the group consisting of diatomaceous earth, feldspar, pottery, lime, milky, and combinations thereof. The content of the additive is not particularly limited, and may be appropriately employed within a range in which the function of the porous ceramic tile is not impaired.
구체적으로, 상기 다공성 세라믹 타일은 총 100중량%에 대해서 상기 첨가물을 약 5중량%이하, 구체적으로 약 3중량%이하를 포함할 수 있다. 상기 함유함량의 첨가제를 포함함으로써 γ-알루미나, 유리질 결합물질 및 모물질 함량을 적절하게 조절할 수 있어, 상기 다공성 세라믹 타일의 성형강도, 소성강도 등의 물리적 안정성 및 흡방습성의 기능을 일정수준 유지할 수 있다. Specifically, the porous ceramic tile may include about 5% by weight or less of the additive, specifically about 3% by weight or less, based on 100% by weight. By including the content of the additive, the content of γ-alumina, glassy binder and parent material can be adjusted appropriately, so that the function of physical stability and moisture absorption and moisture resistance of the porous ceramic tile such as molding strength and plastic strength can be maintained at a certain level. have.
상기 첨가물 중 규조토는 흡수성이 풍부한 다공질로서, 다공성 세라믹 타일 형성에 첨가되는 경우, 흡습 기능을 보다 향상시킬 수 있고, 기타 규석, 장석, 도석 및 석회 등도 각각 적절한 양으로 내에 포함될 수 있다. 아울러, 상기 유백제는 유리 제품에 흰빛이 나게 하기 위하여 첨가하는 분말로서, 그 종류가 특별히 제한되는 것은 아니지만, 염화물, 주석, 티타늄 산화물, 황산염, 인산염, 비산염 및 불화물로 이루어진 군에서 선택된 하나 이상을 포함할 수 있다.Diatomaceous earth in the additive is a porous, rich in water absorption, when added to the porous ceramic tile formation can further improve the hygroscopic function, and other silica, feldspar, stone and lime can also be included in the appropriate amount. In addition, the whitening agent is a powder added to give a white color to the glass product, the type is not particularly limited, but at least one selected from the group consisting of chloride, tin, titanium oxide, sulfate, phosphate, arsenate and fluoride It may include.
상기 다공성 세라믹 타일의 굽힘강도는 약 10MPa 내지 약 20MPa일 수 있다. 굽힘강도는 굽힘시험에서 파괴시의 최대 인장응력을 일컫는바, 다공성 세라믹 타일에 굽힘압력을 가했을 때 다공성 세라믹 타일 파괴시의 최대 인장응력을 의미한다. 통상의 다공성 세라믹 타일의 굽힘강도는 약 10Mpa 미만의 굽힘강도를 가지는 것으로 측정되나, 상기 다공성 세라믹 타일은 바인더 역할을 하는 유리질 결합물질을 약 5중량% 내지 약 20중량% 포함함으로써, 통상의 다공성 세라믹 타일의 굽힘강도에 비해 약 100%이상 향상된 굽힘강도를 확보할 수 있다. The bending strength of the porous ceramic tile may be about 10 MPa to about 20 MPa. Bending strength refers to the maximum tensile stress at break in bending test, which means the maximum tensile stress at break of porous ceramic tile when bending pressure is applied to the porous ceramic tile. The bending strength of a conventional porous ceramic tile is measured to have a bending strength of less than about 10 Mpa, but the porous ceramic tile includes about 5% by weight to about 20% by weight of glassy binder, which acts as a binder, thereby providing a general porous ceramic. It can secure the bending strength improved by about 100% more than the bending strength of the tile.
다공성 세라믹이 아닌 일반 세라믹 타일의 굽힘강도는 약 20MPa 정도이며 이 경우 운송 및 시공 중 파손이 극히 드물게 발생하므로 이를 적절한 강도의 기준으로 삼는 것이 보통이다. 그러므로, 상기 다공성 세라믹 타일의 굽힘강도는 일반 세라믹 타일의 굽힘강도와 유사한 바, 다공성 세라믹 타일 제작, 운송 및 시공시에 발생하는 물리적 충격에 의한 파손, 크랙 생산 등을 최소화할 수 있고, 손실률을 줄일 수 있어, 생산단가를 줄이고 시공속도를 향상시킬 수 있다. The bending strength of general ceramic tiles other than porous ceramics is about 20MPa. In this case, breakage occurs rarely during transportation and construction. Therefore, the bending strength of the porous ceramic tile is similar to the bending strength of the general ceramic tile, thereby minimizing damage, crack production, etc. due to physical shocks generated during the production, transportation, and construction of the porous ceramic tile, and reducing the loss rate. Can reduce the production cost and improve the construction speed.
상기 다공성 세라믹 타일의 흡방습량은 약 60g/m2 내지 약 100g/m2일 수 있다. 상기 다공성 세라믹 타일의 흡방습량은 인간이 가장 쾌적한 생활을 할 수 있다는 중습영역(온도 약 25℃, 상대습도 약 50% 내지 약 75%)에서 습도를 조절하기 위해 필요한바, 상기 타일의 흡습량과 방습량의 평균으로 계산할 수 있다. 상기 타일의 흡방습량이 상기 범위를 유지함으로써 습기로 인한 불쾌지수를 최소화할 수 있고, 상기 타일에 곰팡이 및 세균 발생을 억제할 수 있다.Moisture absorption and moisture absorption of the porous ceramic tile may be about 60g / m 2 to about 100g / m 2 . Moisture absorption and moisture absorption of the porous ceramic tile is necessary to control the humidity in the medium-humidity region (temperature about 25 ℃, relative humidity about 50% to about 75%) that humans can live the most comfortable life, the moisture absorption amount of the tile Can be calculated as the average of the amount of moisture and moisture. By maintaining the moisture absorption and moisture content of the tile, the discomfort index due to moisture can be minimized, and mold and bacteria can be suppressed in the tile.
또한, 상기 다공성 세라믹 타일은 약 15중량% 내지 약 60중량%의 γ-알루미나를 포함하는바, 다공성 세라믹 타일 형성 입자 표면에 일정수준 이상의 공극률을 가지는 기공을 포함할 수 있다. 또한, 유리질 결합물질을 함께 포함함에도 불구하고, 상기 γ-알루미나의 함유함량 조절과 동시에 유리질 결합물질 함유함량을 조절하는바, 공기의 입출입을 원활하게 하기 위한 일정크기의 다공성 세라믹 타일 형성 입자 사이의 기공을 확보할 수 있다. In addition, the porous ceramic tile may include about 15 wt% to about 60 wt% of γ-alumina, and may include pores having a predetermined porosity or more on the surface of the porous ceramic tile forming particle. In addition, despite the inclusion of a glassy binder, the content of the γ-alumina and at the same time to control the content of the glassy binder material, between the porous ceramic tile-forming particles of a certain size to facilitate the entry and exit of air Pore can be secured.
도 1은 본 발명의 일실시예인 다공성 세라믹 타일을 도식화 하여 나타낸 것이다. 상기 다공성 세라믹 타일은 상기 유리질 결합물질에 의해 연결된 다공성 세라믹 타일 형성입자를 포함할 수 있다. 1 is a schematic view showing a porous ceramic tile of an embodiment of the present invention. The porous ceramic tile may include porous ceramic tile forming particles connected by the glassy binder.
구체적으로, 다공성 세라믹 타일 형성 입자가 유리질 결합물질에 의해 연결될 수 있고, 상기 다공성 세라믹 타일 형성입자 표면에 미세기공, 상기 다공성 세라믹 타일 형성입자간 사이에 열린기공을 포함할 수 있다. 또한, 상기 다공성 세라믹 타일 형성 입자는 미세기공과 동시에 유리질 결합물질에 의해 막힌 미세기공을 포함 할 수 있고, 각각의 물질의 함량을 조절하여 굽힘강도 및 흡방습성이 최적화되게 할 수 있다. Specifically, the porous ceramic tile forming particles may be connected by a glassy binder material, and may include micropores on the surface of the porous ceramic tile forming particles and open pores between the porous ceramic tile forming particles. In addition, the porous ceramic tile-forming particles may include micropores blocked at the same time as the micropore and the glassy binding material, it is possible to optimize the bending strength and moisture absorption by adjusting the content of each material.
상기 다공성 세라믹 타일은 종래의 다공성 세라믹 타일을 도식화 하여 나타낸 도 2와 비교하여, 다공성 세라믹 타일을 형성하는 γ-알루미나 및 유리질 결합물질의 함량을 조절하여 포함하는바, 유리질 결합물질이 바인더 역할을 더 견고히 함으로써 종래의 다공성 세라믹 타일에 비해 보다 높은 강도를 확보할 수 있다. The porous ceramic tile is compared with FIG. 2 shown in a schematic diagram of a conventional porous ceramic tile, by controlling the content of the γ-alumina and the glassy binder forming the porous ceramic tile, the glassy binder further serves as a binder By strengthening, it is possible to secure a higher strength than conventional porous ceramic tiles.
상기 다공성 세라믹 타일 형성입자의 기공률은 약 30% 내지 약 50%일 수 있다. 구체적으로, 다공성 세라믹 타일 형성입자의 표면에 분포된 미세기공과 다공성 세라믹 타일 형성입자 사이에 형성된 열린기공의 기공률을 의미하는바, 상기 기공률은 상기 미세기공 및 열린기공의 공극의 정도를 나타내는 수치, 즉 상기 기공률은 다공성 타일 형성 입자의 전 부피에 대한 타일 내부의 열린기공 및 미세기공 부피의 백분율을 의미한다. The porosity of the porous ceramic tile forming particles may be about 30% to about 50%. Specifically, the porosity of the open pores formed between the micropores distributed on the surface of the porous ceramic tile forming particles and the porous ceramic tile forming particles, the porosity is a numerical value representing the degree of the pores of the micropores and open pores, that is, The porosity refers to the percentage of open pore and micropore volume inside the tile to the total volume of the porous tile forming particles.
상기 다공성 세라믹 타일이 γ-알루미나 외에 유리질 결합물질을 포함하는바, 상기 유리질 결합물질에 의해 막힌 미세기공이 발생할 수 있으나, 상기 γ-알루미나 및 유리질 결합물질의 함량을 조절함으로써, 상기 범위의 기공률을 유지할 수 있고, 이로 인해 높은 조습기능에 기인한 우수한 습도조절 효과를 용이하게 구현할 수 있다. Since the porous ceramic tile includes a glassy binder in addition to γ-alumina, micropores may be blocked by the glassy binder, but by controlling the content of the γ-alumina and the glassy binder, the porosity in the range may be adjusted. It is possible to maintain, and thus it is possible to easily implement the excellent humidity control effect due to the high humidity control function.
상기 다공성 세라믹 타일은 평균 직경이 약 0.5㎛ 내지 약 50㎛인 기공을 포함할 수 있다. 구체적으로, 상긴 기공은 상기 다공성 세라믹 타일 형성입자 사이에 형성된 기공으로, 열린기공이라고도 하며, 공기의 입출입을 원활하게 하기 위한 공간을 의미한다. 보다 구체적으로, 상기 기공의 평균 직경은 상기 열린 기공 직경의 산술적인 평균치를 일컫는다.The porous ceramic tile may include pores having an average diameter of about 0.5 μm to about 50 μm. Specifically, the upper pores are pores formed between the porous ceramic tile-forming particles, also called open pores, and mean spaces for smoothly entering and exiting air. More specifically, the mean diameter of the pores refers to an arithmetic mean value of the open pore diameters.
상기 다공성 세라믹 타일이 유리질 결합물질을 포함함으로써 바인더 또는 접착제 역할을 수행함으로써, 종래의 다공성 세라믹 타일의 열린기공에 비해 상대적으로, 작아진 열린기공의 평균직경을 가지나, 상기 유리질 결합물질의 함유함량을 조절하는바, 상기 범위 내의 열린기공 평균 직경을 유지할 수 있고, 이로 인해 공기 및 수분 등이 입출입 하기에 원활한 흐름을 확보할 수 있고, 타일의 강도가 높게 유지됨으로써 타일 내부의 미세 기공을 갖는 γ-알루미나의 상대량이 일정하게 유지되어 조습기능을 확보할 수 있다. Since the porous ceramic tile serves as a binder or an adhesive by including a glassy binder material, the porous ceramic tile has a smaller average diameter of open pores, compared to the open pores of a conventional porous ceramic tile, but the content of the glassy binder material is increased. It is possible to maintain the average diameter of the open pores within the above range, thereby ensuring a smooth flow for entering and entering the air and moisture, and the strength of the tile is maintained high γ- having fine pores inside the tile The relative amount of alumina is kept constant to ensure the humidity control function.
구체적으로, 상기 다공성 세라믹 타일은 평균 직경이 약 1nm 내지 약 50nm인 기공을 포함할 수 있다. 이때, 상기 기공은 타공성 세라믹 타일 형성입자의 표면에 분포된 미세기공일 수 있고, 미세기공이 상기 범위의 평균 직경을 유지함으로 타일의 강도를 높게 유지할 수 있고, 조습기능 또한 확보할 수 있다. In detail, the porous ceramic tile may include pores having an average diameter of about 1 nm to about 50 nm. In this case, the pores may be micropores distributed on the surface of the porous ceramic tile-forming particles, the micropores can maintain a high strength of the tile by maintaining the average diameter of the range, it is also possible to ensure the humidity control function.
그러므로, 상기 다공성 세라믹 타일은 상기 유리질 결합물질 및 상기 γ-알루미나를 동시에 일정함량 포함함으로써, 상기 다공성 세라믹 타일의 강도 및 흡방습성을 함께 확보할 수 있다. Therefore, the porous ceramic tile includes both the glassy binder and the γ-alumina at the same time, thereby ensuring both strength and moisture absorption and moisture absorption of the porous ceramic tile.
이하에서는 본 발명의 구체적인 실시예들을 제시한다. 다만, 하기에 기재된 실시예들은 본 발명을 구체적으로 예시하거나 설명하기 위한 것에 불과하며, 이로서 본 발명이 제한되어서는 아니된다.The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.
<실시예 및 비교예><Examples and Comparative Examples>
하기 표 1에 기재된 고형 성분들의 혼합물을 총량(%) 대비 물을 약 20~50% 추가하여 볼밀을 통해 분쇄하고, 이에 따라 얻어진 슬러리를 분무건조 공정을 통해 균일하게 혼합되고 함수율이 8%, 평균입도 300㎛인 구형의 과립분말을 제조하였다. 이 때, 상기 제조된 과립분말은 하기 표 2에 기재된 고형 성분들을 포함한다. The mixture of the solid components shown in Table 1 is pulverized through a ball mill by adding about 20-50% of water to the total amount (%), and the slurry thus obtained is uniformly mixed through a spray drying process and the water content is 8%, average A spherical granular powder having a particle size of 300 μm was prepared. At this time, the prepared granulated powder includes the solid components shown in Table 2 below.
이어서, 상기 과립분말을 건식 프레스 성형하여 가로, 세로, 두께가 각각 5cm, 5cm, 0.6cm인 다공성 세라믹 타일을 제조하였다. 다음으로 전기 가열로(Furnace)에 투입하여 850℃의 온도로 5분 동안 소성하여 다공성 세라믹 타일을 제조하였다.Subsequently, the granular powder was dry press-molded to prepare porous ceramic tiles having a width, length, and thickness of 5 cm, 5 cm, and 0.6 cm, respectively. Next, it was put in an electric furnace (Furnace) and baked for 5 minutes at a temperature of 850 ℃ to prepare a porous ceramic tile.
구체적으로, 제조과정 중 수산화알루미늄(Al(OH)3)은 γ-알루미나(Al2O3)로, 탄석(CaCO3)은 생석회(CaO)로 변화하는바, 수산화알루미늄의 γ-알루미나 전환율은 약 0.6 내지 약 0.7이며, 탄석의 생석회 전환율은 약 0.5 내지 약 0.6일 수 있는바, 하기 표 1 및 2에서 수산화알루미늄의 γ-알루미나 전환율은 0.654, 탄석의 생석회 전환율은 0.56이었다. In detail, aluminum hydroxide (Al (OH) 3 ) is converted into γ-alumina (Al 2 O 3) and calcined coal (CaCO 3) into quicklime (CaO) during the manufacturing process, and the γ-alumina conversion of aluminum hydroxide is about 0.6 to about. 0.7, and the quicklime conversion of the coal can be about 0.5 to about 0.6. In Tables 1 and 2, the γ-alumina conversion of aluminum hydroxide is 0.654 and the quicklime conversion of the coal is 0.56.
표 1
점토 수산화알루미늄 유리 프리트 규석 산청토 탄석 안료 합계
실시예1 46.2 19.6 11 1.5 2.2 17.7 0.8 100
실시예2 39.6 29.3 11 1.3 1.9 15.2 0.7 100
실시예3 37.6 29.3 14 1.2 1.8 14.4 0.7 100
실시예4 31 39.1 14 1 1.5 11.9 0.5 100
실시예5 35.5 29.3 15.5 1.1 1.7 13.6 0.8 100
실시예6 28.9 39.1 15.5 0.9 1.4 11.1 0.6 100
비교예1 56 10 17.5 0.9 1.4 11.1 0.6 100
비교예2 16 70 5 0.9 1.4 11.1 0.6 100
비교예3 33 50 3 0.9 1.4 11.1 0.6 100
비교예4 41 20 25 0.9 1.4 11.1 0.6 100
Table 1
clay Aluminum hydroxide Glass frit burr Sancheong soil Charcoal Pigment Sum
Example 1 46.2 19.6 11 1.5 2.2 17.7 0.8 100
Example 2 39.6 29.3 11 1.3 1.9 15.2 0.7 100
Example 3 37.6 29.3 14 1.2 1.8 14.4 0.7 100
Example 4 31 39.1 14 One 1.5 11.9 0.5 100
Example 5 35.5 29.3 15.5 1.1 1.7 13.6 0.8 100
Example 6 28.9 39.1 15.5 0.9 1.4 11.1 0.6 100
Comparative Example 1 56 10 17.5 0.9 1.4 11.1 0.6 100
Comparative Example 2 16 70 5 0.9 1.4 11.1 0.6 100
Comparative Example 3 33 50 3 0.9 1.4 11.1 0.6 100
Comparative Example 4 41 20 25 0.9 1.4 11.1 0.6 100
표 2
점토 γ-알루미나 유리 프리트 규석 산청토 생석회 안료 합계
실시예1 54.7 15.2 13.0 1.8 2.6 11.7 0.9 100
실시예2 48.2 23.3 13.4 1.6 2.3 10.4 0.9 100
실시예3 45.6 23.2 17.0 1.5 2.2 9.8 0.8 100
실시예4 38.6 31.9 17.4 1.2 1.9 8.3 0.6 100
실시예5 43.6 23.5 19.0 1.4 2.1 9.4 1.0 100
실시예6 36.5 32.3 19.6 1.1 1.8 7.9 0.8 100
비교예1 62.8 7.3 19.6 1.0 1.6 7.0 0.7 100
비교예2 21.1 60.3 6.6 1.2 1.8 8.2 0.8 100
비교예3 42.4 42.0 3.9 1.2 1.8 8.0 0.8 100
비교예4 46.5 14.8 28.3 1.0 1.6 7.0 0.7 100
TABLE 2
clay γ-alumina Glass frit burr Sancheong soil quicklime Pigment Sum
Example 1 54.7 15.2 13.0 1.8 2.6 11.7 0.9 100
Example 2 48.2 23.3 13.4 1.6 2.3 10.4 0.9 100
Example 3 45.6 23.2 17.0 1.5 2.2 9.8 0.8 100
Example 4 38.6 31.9 17.4 1.2 1.9 8.3 0.6 100
Example 5 43.6 23.5 19.0 1.4 2.1 9.4 1.0 100
Example 6 36.5 32.3 19.6 1.1 1.8 7.9 0.8 100
Comparative Example 1 62.8 7.3 19.6 1.0 1.6 7.0 0.7 100
Comparative Example 2 21.1 60.3 6.6 1.2 1.8 8.2 0.8 100
Comparative Example 3 42.4 42.0 3.9 1.2 1.8 8.0 0.8 100
Comparative Example 4 46.5 14.8 28.3 1.0 1.6 7.0 0.7 100
<실험예> - 다공성 세라믹 타일의 흡방습성 및 굴곡강도 측정 Experimental Example-Measurement of Moisture Absorption and Flexural Strength of Porous Ceramic Tiles
상기 실시예 및 비교예의 다공성 세라믹 타일의 흡방습성 및 굴곡강도를 측정하였고, 그 결과를 하기 표 3에 나타내었다.Moisture absorption and flexural strength of the porous ceramic tiles of Examples and Comparative Examples were measured, and the results are shown in Table 3 below.
1) 흡방습량: 25℃의 온도 및 상대습도(Relative Humidity, RH) 50%의 조건에서 24시간 동안 상기 실시예 및 비교예의 다공성 세라믹 타일을 방치한 후, 다시 25℃의 온도 및 RH 75%의 조건에서 12시간 동안 유지하여 무게차이를 측정하고, 다시 25℃의 온도 및 RH 50%의 조건에서 12시간 동안 유지한 후, 무게차이를 측정하여 그 평균값을 단위 면적으로 환산하여 계산하였다. 1) Moisture absorption and moisture content: After leaving the porous ceramic tiles of the above Examples and Comparative Examples for 24 hours at a temperature of 25 ℃ and 50% Relative Humidity (RH), the temperature of 25 ℃ and RH 75% The weight difference was measured by maintaining for 12 hours under the condition of, and then maintained for 12 hours under the condition of 25 ° C. and 50% RH, and then the weight difference was measured to calculate the average value in terms of unit area.
2) 굴곡강도: 굴곡강도를 측정하여 위해 3점 굽힘 강도법을 사용하였는바, 약 가로, 세로가 각각 5cm, 5cm, 높이가 0.5cm인 직육면체 모양의 타일을 3개씩 만든 후 파괴가 일어날 때까지 힘을 가하여 굽힘 강도를 측정하였다.2) Flexural Strength: The three-point bending strength method was used to measure the flexural strength. Three rectangular tiles, 5 cm, 5 cm, and 0.5 cm in width and length, respectively, were made, and then flexing strength was applied until fracture occurred. Was measured.
상기 굽힘 강도는 (3PL)/(2wt^2)에 의해 계산되고, 이때, P는 타일이 파괴되었을 때의 최대 하중, L은 외부간격, w는 타일의 폭, t는 타일의 두께이다. The bending strength is calculated by (3PL) / (2wt ^ 2), where P is the maximum load when the tile is broken, L is the outer gap, w is the width of the tile, and t is the thickness of the tile.
표 3
흡방습량(g/m2) 강도(MPa) 흡방습량(g/m2) 강도(MPa)
실시예1 70 10.8 비교예1 46 16.8
실시예2 86 11.1 비교예2 125 소성중파괴
실시예3 83 13.8 비교예3 67 4.2
실시예4 109 10.6 비교예4 90 소성중파괴
실시예5 71 16.4
실시예6 96 13.4
TABLE 3
Moisture absorption and moisture absorption (g / m 2 ) Strength (MPa) Moisture absorption and moisture absorption (g / m 2 ) Strength (MPa)
Example 1 70 10.8 Comparative Example 1 46 16.8
Example 2 86 11.1 Comparative Example 2 125 Destruction during firing
Example 3 83 13.8 Comparative Example 3 67 4.2
Example 4 109 10.6 Comparative Example 4 90 Destruction during firing
Example 5 71 16.4
Example 6 96 13.4
상기 표 2 및 표 3를 참고하면, 실시예 1 내지 6은 γ-알루미나 15중량% 내지 60중량% 및 유리 프리트 5중량% 내지 20중량%를 포함하여 형성된 다공성 타일로써, 굴곡강도의 경우 약 10MPa 내지 약 20MPa 범위 내로 측정되고, 흡방습성을 나타내는 평량은 약 60g/m2 이상을 나타내었는바, 상기 다공성 세라믹 타일이 유리질 결합물질 및 γ-알루미나의 함량조절에 따라 굴곡강도 및 흡방습성을 동시에 확보함을 유추할 수 있었다. Referring to Tables 2 and 3, Examples 1 to 6 are porous tiles formed of 15 wt% to 60 wt% of γ-alumina and 5 wt% to 20 wt% of glass frit, and about 10 MPa for flexural strength. The basis weight, which is measured in the range of about 20 MPa and exhibits moisture absorption and moisture absorption, was about 60 g / m 2 or more. The porous ceramic tile secures flexural strength and moisture absorption at the same time according to the content control of the glassy binder and γ-alumina. Inference could be inferred.
이와 대조적으로, γ-알루미나를 함유함량에 비해 적게 포함한 비교예 1의 경우 굴곡강도는 최적화 되었으나 유리 프릿트가 다공성 타일의 기공들을 막아 흡방습성을 확보하지 못하였고, γ-알루미나를 함유함량에 비해 많이 포함한 비교예 2의 경우, 상대적으로 모물질, 즉 점토의 함량이 낮아져 소성(성형)강도가 감소되어 다공성 세라믹 타일의 제조에 있어서 소성 중에 파괴되었다. In contrast, in the case of Comparative Example 1 containing less than γ-alumina, the flexural strength was optimized, but glass frit did not secure moisture absorption by blocking pores of the porous tile, and compared with γ-alumina content. In the case of Comparative Example 2, which contains a large amount, the content of the parent material, i.e., the clay, was relatively low, so that the plastic (molding) strength was reduced, which was destroyed during firing in the manufacture of the porous ceramic tile.
또한, 유리질 결합물질을 함유함량에 비해 적게 포함한 비교예 3의 경우 γ-알루미나의 함유로 인해 흡방습성을 최적화 되었으나 낮은 유리질 결합물질의 함량에 의해 약한 강도를 가지게 되었고, 유리질 결합물질을 함유함량에 비해 많이 포함한 비교예 4의 경우는 과량의 유리질 결합물질로 인해 소성 중 수축이 심하여 구부러짐에 의해 파괴되었다. In addition, in the case of Comparative Example 3 containing less than the glassy binder content, the moisture absorption and moisture absorption was optimized due to the content of γ-alumina, but had a weak strength due to the content of the low glassy binder material, In the case of Comparative Example 4 containing a lot compared to the fracture due to the excessive shrinkage during firing due to the excessive glassy binder material.

Claims (12)

  1. γ-알루미나 15중량% 내지 60중량% 및 유리질 결합물질 5중량% 내지 20중량%를 포함하는15 to 60% by weight of γ-alumina and 5 to 20% by weight of the glassy binder
    다공성 세라믹 타일.Porous ceramic tile.
  2. 제 1항에 있어서,The method of claim 1,
    상기 γ-알루미나는 질화알루미늄, 탄산알루미늄, 염화알루미늄, 염화알루미늄 이수화물, 수산화알루미늄, 알루미늄클로라이드, 알루미늄 나이트래이트, 알루미나 졸 및 이들의 조합으로 이루어진 군으로부터 선택된 하나의 알루미늄 소스가 상변이된 물질을 포함하는 The γ-alumina is a material having a phase change of one aluminum source selected from the group consisting of aluminum nitride, aluminum carbonate, aluminum chloride, aluminum chloride dihydrate, aluminum hydroxide, aluminum chloride, aluminum nitrate, alumina sol, and combinations thereof Containing
    다공성 세라믹 타일. Porous ceramic tile.
  3. 제 1항에 있어서,The method of claim 1,
    상기 유리질 결합물질은 유리 프리트를 포함하는 The glassy binder comprises glass frit
    다공성 세라믹 타일. Porous ceramic tile.
  4. 제 1항에 있어서,The method of claim 1,
    상기 다공성 세라믹 타일은 총 100중량% 중 모물질을 25중량% 내지 65중량%를 포함하는The porous ceramic tile includes 25% to 65% by weight of the parent material in a total of 100% by weight
    다공성 세라믹 타일.Porous ceramic tile.
  5. 제 4항에 있어서,The method of claim 4, wherein
    상기 모물질은 점토, 백토, 황토 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상을 포함하는 The parent material includes one or more selected from the group consisting of clay, clay, loess and combinations thereof.
    다공성 세라믹 타일. Porous ceramic tile.
  6. 제 1항에 있어서,The method of claim 1,
    규조토, 장석, 도석, 석회, 유백제 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상의 첨가물을 추가로 포함하는 Further comprising one or more additives selected from the group consisting of diatomaceous earth, feldspar, pottery, lime, milky and combinations
    다공성 세라믹 타일. Porous ceramic tile.
  7. 제 6항에 있어서,The method of claim 6,
    상기 다공성 세라믹 타일은 총 100중량%에 대해서 상기 첨가물을 5중량% 이하 포함하는The porous ceramic tile includes 5 wt% or less of the additive based on 100 wt% of the total.
    다공성 세라믹 타일.Porous ceramic tile.
  8. 제 1항에 있어서,The method of claim 1,
    상기 다공성 세라믹 타일의 굽힘강도는 10MPa 내지 20MPa인The bending strength of the porous ceramic tile is 10MPa to 20MPa
    다공성 세라믹 타일.Porous ceramic tile.
  9. 제 1항에 있어서,The method of claim 1,
    상기 다공성 세라믹 타일의 흡방습량이 60g/m2 내지 100g/m2인Moisture absorption and moisture absorption of the porous ceramic tile is 60g / m 2 to 100g / m 2
    다공성 세라믹 타일.Porous ceramic tile.
  10. 제 1항에 있어서,The method of claim 1,
    상기 다공성 세라믹 타일은 상기 유리질 결합물질에 의해 연결된 다공성 세라믹 타일 형성입자를 포함하는The porous ceramic tile includes porous ceramic tile forming particles connected by the glassy binder.
    다공성 세라믹 타일. Porous ceramic tile.
  11. 제 10항에 있어서,The method of claim 10,
    상기 다공성 세라믹 타일 형성입자의 기공률이 30% 내지 50%인 The porosity of the porous ceramic tile forming particles is 30% to 50%
    다공성 세라믹 타일.Porous ceramic tile.
  12. 제 1항에 있어서,The method of claim 1,
    상기 다공성 세라믹 타일은 평균 직경이 0.5㎛ 내지 50㎛인 기공을 포함하는The porous ceramic tile includes pores having an average diameter of 0.5 ㎛ to 50 ㎛
    다공성 세라믹 타일.Porous ceramic tile.
PCT/KR2014/004860 2013-05-31 2014-05-30 Porous ceramic tile with high strength and high hygroscopic and desiccative properties WO2014193192A1 (en)

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Applications Claiming Priority (2)

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KR1020130062705A KR101731139B1 (en) 2013-05-31 2013-05-31 Porous ceramic tile having high strength and high moisture-absorbing
KR10-2013-0062705 2013-05-31

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KR102400074B1 (en) * 2020-02-28 2022-05-23 (주)다대메이커스 Manufacturing method of durable ceramic tile

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JP2003176128A (en) * 2001-12-06 2003-06-24 Toto Ltd Humidity control building material and humidity control material
JP2006232650A (en) * 2005-02-24 2006-09-07 Entec Kk Porous structure lightweight ceramics, antibacterial porous structure lightweight ceramics, water stop and waterproof porous structure lightweight ceramics, waterproof porous structure lightweight ceramics, snow melting porous structure lightweight ceramics and their manufacturing methods
KR20110068207A (en) * 2009-12-15 2011-06-22 (주)엘지하우시스 Ceramic material having humidity controlling performance, preparing method thereof and ceramic tile using the same
KR20120111048A (en) * 2011-03-31 2012-10-10 (주)엘지하우시스 High porous ceramic structure for frost and dew prevention and refrigerator including the high porous ceramic structure

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JP2000070659A (en) * 1998-09-02 2000-03-07 Sharp Corp Dehumidifying material and dehumidifier
JP2003176128A (en) * 2001-12-06 2003-06-24 Toto Ltd Humidity control building material and humidity control material
JP2006232650A (en) * 2005-02-24 2006-09-07 Entec Kk Porous structure lightweight ceramics, antibacterial porous structure lightweight ceramics, water stop and waterproof porous structure lightweight ceramics, waterproof porous structure lightweight ceramics, snow melting porous structure lightweight ceramics and their manufacturing methods
KR20110068207A (en) * 2009-12-15 2011-06-22 (주)엘지하우시스 Ceramic material having humidity controlling performance, preparing method thereof and ceramic tile using the same
KR20120111048A (en) * 2011-03-31 2012-10-10 (주)엘지하우시스 High porous ceramic structure for frost and dew prevention and refrigerator including the high porous ceramic structure

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KR101731139B1 (en) 2017-04-27

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