JPH02317B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing decorative tiles, and more particularly to a method for manufacturing decorative tiles with specular luster. Traditionally, tiles have been used as wall and floor materials for buildings, particularly in bathrooms, which require water resistance, but in recent years they have also been used for decoration on the exteriors of buildings, and have changed from just colored tiles to Furthermore, there is a demand for highly decorative tiles, and various decorative tiles such as patterned tiles have been proposed. On the other hand, it is well known that when natural light is applied to a material made of multiple layers of thin films with different refractive indexes and absorption wavelengths, specific wavelengths are reflected more strongly due to light interference, producing a unique specular luster. There is. However, decorative tiles with such mirror gloss are not known. An object of the present invention is to provide a method for manufacturing a decorative tile with specular luster. As a result of intensive research to achieve the above object, the present inventors applied a multilayer organic metal compound of the same or different metals on the surface of a smooth magnetic tile substrate, and then heated and fired the metal. The present invention was completed by discovering that a multilayer coating of metal oxide thin films can be easily formed on the tile substrate. The present invention is a decoration characterized by forming a multilayer transparent metal oxide thin film by applying an organic metal compound in multiple layers on the surface of a porcelain tile substrate and then firing it at a temperature of 300°C to 1000°C. This is a method for manufacturing tiles. In the present invention, the metal oxide thin film is a stable and transparent thin film of an oxide of a metal belonging to Group 1 or Group 3 of the periodic table of elements. In the present invention, the decorative tile is formed by forming multiple layers, preferably 2 to 5 layers, of the same kind and different kinds of metal oxides on the surface of a porcelain tile substrate. For example, TiO ₂ /SuO ₂ /TiO ₂ , SiO ₂ /
This is a decorative tile with a multilayer metal oxide thin film such as FeO/TiO ₂ , TiO ₂ /Ta ₂ O ₅ /SiO ₂ /TiO ₂ formed on the surface. In the present invention, the porcelain tile substrate may be unglazed, overglazed, or made by pressing and sintering ceramic particles. The tiles obtained by the present invention may be formed by forming a multilayer thin film of the metal oxide on a magnetic tile substrate by vacuum evaporation, sputtering, etc., but mass production is difficult when using these electronic material manufacturing methods. and is not economically viable. Therefore, in the present invention, it is produced by the following method. Organometallic compounds of desired metals, such as alkoxides of the metals such as impropoxides and butoxides, and chain-like products of partial hydrolysis of the alkoxides with water or acids are coated on the smooth surface of the porcelain tile substrate. and/or cyclic polymers, alkoxides and/or chelate complexes in which part or all of the alkoxy groups of the polymers are substituted with a chelating agent, and one or more polymers thereof alone or dissolved in a solvent. It can be produced by repeating coating and drying in multiple layers in a desired order, followed by firing at a temperature of 300 to 1000°C, preferably 350 to 700°C. Examples of the chelating agent include β-diketones such as acetylacetone and benzoylacetone, ketone acids and their esters such as acetoacetic acid, propionylbutyric acid, and benzoylformic acid, and oxyacids such as lactic acid, glycolic acid, α-oxybutyric acid, and salicylic acid. and its esters, diacetone alcohol, oxyketones such as acetoin, α-amino acids such as glycine and alanine, amino alcohols such as aminoethyl alcohol, etc. These also serve as solvents for the metal compounds such as alcohols, It can be used together with esters, ethers, hydrocarbons, halogenated hydrocarbons, etc. As a method for applying the organometallic compound to the surface of the magnetic tile substrate, any method capable of forming a uniform thin film, such as a spray method, a spinner method, a dipping method, or a pyrosol method, can be used. The method for manufacturing decorative tiles according to the present invention
A decorative tile on which a three-layer thin film of TiO ₂ /SiO ₂ /TiO ₂ is formed will be described in detail as an example. Alkoxides of titanium, such as tetrabutoxytitanium, which is a product of partial hydrolysis with water, of polymers containing 1 to 10 wt% of _TiO2 , β-diketones, such as acetone, and alkoxides of silicon, such as tetraisopropoxysilane, and mineral acids. A small amount of phosphorus pentoxide is added to a lower alcohol-acetic acid solution containing 1 to 12 wt% SiO ₂ equivalent of a partially hydrolyzed and polymerized siloxane compound as a catalyst to prepare a solution. This adjusted solution was applied to the smooth surface of the porcelain tile surface in the order of Ti solution, Si solution, and Ti solution, and was then dried repeatedly.
TiO ₂ /
A decorative tile with a three-layer thin film of SiO ₂ /TiO ₂ is produced. The present invention focuses on the types of metal oxides to be combined, the number of layers,
By changing the thickness of each thin layer, various colors can be mirror-reflected, and by changing the thickness within a single layer, patterns can be formed. Decoration with extremely diverse specular luster. The present invention provides a method for manufacturing tiles. Hereinafter, it will be explained in detail using examples. Examples 1 to 11 Preparation of Γ organic titanium compound solution 10 parts by weight of an organic titanium polymer with an average degree of polymerization of 10 obtained by partially hydrolyzing tetra-n-butoxytitanium was mixed with methanol:acetylacetone:ethyl acetate = 36.5:10:15 ( In a solution with a _TiO2 concentration of 4.8% by weight (weight ratio),
P ₂ O ₅ corresponding to 2% by weight in terms of TiO ₂ was added to prepare an organic titanium compound solution. Preparation of Γ organosilicon compound solution 219 parts by weight of tetraethoxysilane, 643 parts by weight of ethanol, 206 parts by weight of acetic acid and 0.3 parts by weight of hydrochloric acid were mixed and reacted under reflux for 45 hours.
P ₂ O ₅ corresponding to 2.5% by weight in terms of SiO ₂ was added to an organosilicon compound solution having a concentration in terms of SiO ₂ of 5.9% by weight to prepare an organosilicon compound. Preparation of Γ organic tantalum compound solution Add 10 parts by weight of acetylacetonate tantalum to ethanol:acetylacetone=29:15 (weight ratio)
An organic tantalum compound solution having a concentration of 6.0% by weight in terms of Ta ₂ O ₅ was prepared by dissolving it in a mixed solution of . Method for producing Γ decorative tiles Various combinations of the above organometallic compound solutions were applied to the smooth surface of the decorative tile substrate.
Decorative tiles with 3 to 5 layers of metal oxide thin films were obtained by firing at a temperature of ~500°C, and their properties were measured. The results are shown in Table 1. 【table】

Claims (1)

[Claims] 1. The method is characterized in that a multilayer organic metal compound is applied to the surface of a porcelain tile substrate and then fired at a temperature of 300°C to 1000°C to form a multilayered transparent metal oxide thin film. A method for manufacturing decorative tiles. 2 Organometallic compounds include alkoxides of the metals, polymers obtained by partial hydrolysis of the alkoxides, chelate complexes in which part or all of the alkoxy groups of the alkoxides are substituted with chelating agents, and polymers thereof. 2. The method for producing a decorative tile according to claim 1, wherein one or more types of decorative tiles are used.