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WO2015112101A1 - A coating composition developed for porous surfaces and a method for preparing and applying this composition to surfaces - Google Patents

A coating composition developed for porous surfaces and a method for preparing and applying this composition to surfaces Download PDF

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Publication number
WO2015112101A1
WO2015112101A1 PCT/TR2014/000511 TR2014000511W WO2015112101A1 WO 2015112101 A1 WO2015112101 A1 WO 2015112101A1 TR 2014000511 W TR2014000511 W TR 2014000511W WO 2015112101 A1 WO2015112101 A1 WO 2015112101A1
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WIPO (PCT)
Prior art keywords
composition
acid
composition according
general formula
particles
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Application number
PCT/TR2014/000511
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French (fr)
Inventor
Ayşe TUNALI
Neslihan TAMSU SELLI
Esin Burunkaya
Murat Akarsu
Ertuğrul ARPAÇ
Original Assignee
Eczacibaşi Yapi Gereçleri Sanayi Ve Ticaret Anonim Şirketi
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Publication of WO2015112101A1 publication Critical patent/WO2015112101A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/84—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages

Definitions

  • the subject matter of the invention relates to a filling material/coating composition which can penetrate into and fill in the pores on surfaces by melting upon being applied on porous surfaces, e.g. on the surfaces of the tiles and to a method developed for preparing and applying said coating/filling material to surfaces and products/surfaces comprising the composition prepared according to the invention.
  • Tile is a floor covering material which is commonly used in public and private living spaces, e.g. schools, hospitals, shopping malls, restaurants, kitchens, and bathrooms. It becomes challenging and demanding to clean the stains accumulated on the surface during use as a result of the fact that closed pores therein are opened during polishing processes performed in polished tiles subsequent to production in order to improve the aesthetic appearance.
  • Porcelain tiles have water absorption value less than 0.5% and can be produced by surface embossing, either glazed or unglazed, and they may be defined as white ceramic tiles, or colorful ceramic tiles by the addition of color pigments in starting compositions.
  • Porcelain tiles due to the low water absorption value and highly vitrified structure thereof, are produced at higher temperatures (1200-1220°C) in longer time periods (50-60 minutes) when compared to floor tiles [Biffi, G., Porcelain stoneware - production manual and methods of use, Gruppo Editoriale Faenza Editrice S.p.A., Faenza, 1999].
  • Polished porcelain tiles are the most outstanding ones among porcelain tile types. Polished porcelain tiles have brighter and smoother surfaces than unpolished porcelain tiles; however, the former are significantly poor in wearing and staining resistance (i.e. being stainproof) due to the formation of surface cracks and opening of the closed pores during polishing process [Esposito L, The Reliability of Polished Porcelain Stoware TilesJ. Eur. Cer.Soc.25 (2005) 1487-1498].
  • Such materials provide the surfaces to which they are applied with advantages and properties as follows; delay in becoming dirty, being easy to clean, self-cleaning, reducing water and detergent consumption.
  • That a surface is easy to clean depends on the chemical composition and micro structure of the related surface.
  • the surfaces that are easy to clean are obtained by performing coating with materials with low surface energy, or by improving surface roughness.
  • wax or silicone type constituents used in the present state of the art cover the surfaces with a thin film, rather than filling the pores on the surface, and although they increase staining resistance at first, they are subject to mechanical weathering in the course of time, and thus losing their characteristics.
  • the coating carried out in a way to form a thin film on the tile surface is subject to abrasion after some time, and so its protective effect is lost. Further, since the material remaining on the surface as a film causes surface roughness, the porcelain tiles, which are otherwise expected to have high brightness value, look dull. It is required to rub down the tile to which protective coating is applied having been delivered to the user by using sponge and detergent in order to prevent this appearance. This additional application is not preferred by the user, and also it increases financial losses.
  • the agents comprised therein are inflammable and hazardous to the environment, in addition to having low chemical and mechanical resistance.
  • filling materials which fill in the pores upon melting, rather than coatings are needed in order to prevent such surfaces from getting dirty.
  • the composition having been developed in the present work said composition filling in the pores upon melting, is filled only into the pores, thereby allowing the surface to preserve the bright appearance thereof.
  • the filling material developed within the scope of the invention is an environmentally friendly composition having good chemical and mechanical resistance thanks to the preparation technique and application method thereof.
  • compositions and methods developed for increasing the resistance of the surfaces against dirt/stain formation within the present state of the art are given below.
  • the Patent No. DE102007033398 the resistance is increased by filling the pores on porcelain surfaces with particles comprising fluorosilane and silica addition; however, the composition has a surface dulling effect.
  • a filling material has been developed using fluorine- based silane and some particles; wherein it increases the staining resistance of the surface to which it is applied while reducing the brightness. (Nanoquadrat).
  • the Patent Document No. JP2001294778 discloses a coating which can be applied on the surface as a film and is capable of increasing staining resistance of the surfaces.
  • the composition is known to comprise at least one of the following; colloidal silica, sodium silicate (water glass), and additionally a sodium salt, potassium salt, carbonate or bicarbonate group compounds. It has been stated that said compounds may preferably be Na 2 C0 3 , K 2 C0 3 , NaCI, KCI, KHC0 3 , Na 2 S0 4 and sodium polyphosphate. It has also been pointed out that aluminum silicate, for example, may be used as the compound with aluminum compound.
  • colloidal silica sodium silicate (water glass), and additionally a sodium salt, potassium salt, carbonate or bicarbonate group compounds. It has been stated that said compounds may preferably be Na 2 C0 3 , K 2 C0 3 , NaCI, KCI, KHC0 3 , Na 2 S0 4 and sodium polyphosphate. It has also been pointed out that aluminum silicate, for example,
  • JP2003183581 and JP2005029702 disclose a coating that forms a film on the surface; wherein the composition has the compound with the following formula and X group comprises an alkyl group including amino group, amino alkyl group, vinyl group, epoxy group, glycidoxy group, acrylic group, methacrylic group or sulfhydryl group, but particularly is an amino group.
  • Rl, R2, and R3 groups may be an alkoxy, aryloxy, allyloxy, and halogen group, in addition to OH group, and they may be selected from the groups capable of forming cylanol.
  • the Patent Document No. CN102561627 discloses a tile having a protecting layer and a layer comprising photocatalyst. It has been stated herein that a coating comprising a protecting layer and Ti0 2 , the photocatalyst, thereon is applied on the tile. What has also been disclosed herein is that a thin film layer is formed on the tile surface subsequent to applying the coating comprising photocatalyst on the tile by spraying method; that oil stains, bacteria, and such factors are removed from the surface thanks to the oxygen and oxyhydrogen radicals formed on the surface due to the sunlight; and that dirt and dusts are prevented from adhering onto the surface.
  • the Patent Document No. KR20090063322 discloses a new floor tile with increased surface resistance against stains thanks to the transparent film layer formed on the surface.
  • the Patent Document No. JP2002355917 discloses that a composition comprising titanium oxide and tin oxide with photocatalytic property is applied on a surface, for example a tile surface, and thus the stains are prevented from accumulating on the surface.
  • the Patent Document No. JP2001031483 points out that a coating with photocatalytic property comprising Ti0 2 sol, Si0 2 sol and peroxotitanic acid is applied on the surface in a way to form a film thereon.
  • a filling material which is permanent and environmentally friendly, has high staining resistance, and penetrates into the pores on the surface upon melting and fills in the pores, has been developed.
  • Another advantage provided by the invention is that the tile surfaces maintain their brightness after the polishing process. Since the composition according to the invention does not cause film formation on the surface to which it is applied, it does not have the disadvantages of wearing down and dull appearance of the surface, which are encountered within the present state of the art.
  • Another object of the invention is to develop an environmentally friendly coating composition where silane compounds with no fluorine content are used.
  • Yet another object of the invention is to develop a coating composition which can become hard on the surface to which it is applied, without requiring any thermal treatment. And another object of the invention is to develop a coating composition which does not damage surface brightness on the surface to which it is applied, is easy to clean, and maintains the brightness value of the surface.
  • the subject matter of the invention relates to a filling material/coating composition which can penetrate into and fill in the pores on surfaces by melting upon being applied on porous surfaces, e.g. on the surfaces of the tiles and to a method developed for preparing and applying said coating/filling material to surfaces and products/surfaces comprising the composition prepared according to the invention.
  • Closed pores of different sizes are formed on the surfaces of the polished porcelain tiles during sintering thereof.
  • tile surface is polished using SiC abrasives at the end of firing process. Polishing process causes the surface to hold stains during use since polishing process causes closed pores of 10-50 microns diameter to be exposed.
  • the coating/filling composition according to the invention is developed for preventing the tile surfaces from holding stains and allowing them to be easy to clean.
  • the composition developed according to the invention closes the pores by filling in/penetrating into them, said pores being opened during sintering, after being applied on the surface upon melting; thus, it prevents the surface from holding the stains, at the same time enabling the surface to be easy to clean.
  • the easy-to-clean property of tile surfaces has been analyzed in detail within the scope of the invention depending on the source and concentration of the silane compounds forming the coating/filling material applied on the surface; the source, amount, and particle size of the inorganic particles used in the composition; the source, amount, and particle size of meltable organic particles added into the composition; the amount of water required for hydrolysis in the medium; the duration of hydrolysis- condensation; and on solvent to be used.
  • the easy-to-clean property of tile surfaces where the composition developed within the scope of the invention is applied has been tested according to ISO 10545-14 standard.
  • composition according to the invention mainly comprises at least one silane or mixtures thereof formulas of which have been stated below, at least one type of oxide particle/inorganic particle, and at least one type of organic particle, the general formulas of which have been given below. Additionally, it comprises at least one acid or at least one base which are used for the hydrolysis of silanes and suitable solvent or solvent mixture.
  • composition developed within the scope of the invention comprises at least one silane having the general formula of [R (CH 2 ) n ] m Si(OR') 4-m
  • R group may be alkyl, aryl groups; besides, it may be a functional group comprising epoxy or a functional group comprising double bond of polymerizable methacrylate. Moreover, it may also be acid anhydride, acid halide; amino, hydroxy, mercapto, and isocyano- groups. However, the use of alkyls is preferred most of the time.
  • R' group in the formula may be alkyl, aryl, alkoxy alkyl, or alkoxy aryl groups.
  • silanes comprising methyl, ethyl, and propyl are preferred.
  • the compounds having the above general formula and/or mixtures thereof may be used as functional silane in the composition.
  • the coating composition according to the invention comprises at least one silane having the formula below as tetrafunctional silane, in addition to above mentioned silane compound.
  • Si(OR") R" group in the formula may be alkyl or aryl groups, wherein the use of alkyls, for example methyl, ethyl, propyl, is particularly preferred.
  • the compounds having the general formula of Si(OR") 4 and/or mixtures thereof may be used as tetrafunctional silane in the composition:
  • composition developed within the scope of the invention comprises at least one silane having the general formula of [R (CH 2 ) n ] m Si(OR') 4 . m and at least one silane having the general formula of Si(OR") 4 ; besides, it may comprise the mixtures of these silanes in different rates.
  • the composition prepared within the scope of the invention comprises 30% silane by weight.
  • the compounds such as tetraethyl orthosilicate (tetraethoxysilane), tetramethyl orthosilicate (tetramethoxysilane) and/or the mixtures thereof may be used as the compound having the general formula of Si(OR") 4 , but tetraethyl orthosilicate (tetraethoxysilane) is preferably used; moreover, the silane compound having the general formula of [R (CH 2 ) n ] m Si(OR') .
  • m can be selected from methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octadecyltrimethoxysilane, and hexadecyltrimethoxysilane compounds, but hexadecyltrimethoxysilane is preferably used.
  • the coating composition developed within the scope of the invention comprises oxide particles/inorganic particles, the particle sizes of which are between 1 and 10 ⁇ such that the amounts thereof, in the final mixture will be between 30 and 40% by weight in order for their surfaces to be modified with silanes, in addition to the silanes.
  • the use of Si0 2 , Zr0 2 , Al 2 0 3 and such particles is preferred.
  • the Si0 2 one of the oxide particles, the commercially available products Sikron SF300, SF600, SF800 are preferably used.
  • a single type of inorganic particles can be added into the composition; besides, in the form of mixtures of more than one type of inorganic particles can be used in the composition.
  • the composition developed within the scope of the invention comprises organic particles that provide the material with melting property.
  • the size of the particles to be used is in compliance with that of the pores on the tile surface and the surface where application will be performed. Hydrocarbon wax particles are mostly preferred. It is also possible to use polyethylene or polypropylene wax or teflon (PTFE) or the mixtures thereof within the scope of the invention.
  • the organic particles used within the scope of the invention may be hydrocarbon wax in the form of dispersion and/or in granule form that can melt while being applied on tile surface; likewise, the use of poly tetra fluoro ethylene (PTFE, teflon) modified hydrocarbon wax particles, i.e. particles comprising a layer of PTFE on the surface thereof, is also possible.
  • a single type of organic particles can be used; likewise, it is possible to use the mixture of more than one organic particles.
  • the organic particles added in the composition are done so such that their rates will be 30-40% by weight in the final solid.
  • the organic particles to be used are selected from the products with the trade names DEUTERON-WAX MPO (micronized polyolefin wax), DEUTERON-WAX PP (micronized polypropylene wax), DEUTERON-WAX TF (micronized PTFE-modified polyolefin wax) DEUTERON MM 823 (PTFE-modified micronized plastic), Licolub H4 (Modified hydrocarbon wax), Ceridust 3610 (high density PE), Licocene PP 1302 TP (PP granules, fine grain), Licocene PP 6102 (PP granules, fine grain), Licocene PP 7502 TP (PP granules, fine grain), Ceridust 3831 (Modified polyethylene
  • the composition comprises 20% solvent by weight.
  • the hydrolysis of the silanes used in the composition during the preparation of the composition developed within the scope of the invention is performed at different pH values.
  • hydrochloric acid, phosphoric acid, nitric acid, sulphuric acid, acetic acid, propanoic acid, maleic acid, carbonic acid, citric acid can be used as acid while sodium hydroxide, sodium carbonate, potassium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine can be used as base.
  • the composition comprises at least one acid or base. Acid or base can be added into the mixture in the amount of 1/100 moles of silicium in the silane compound added into the composition.
  • a solution comprising 0.1-50% by weight of at least one type of silane compound having the general formula of Si(OR") 4 and at least one silane compound having the general formula of R(CH 2 ) n ]mSi(OR') 4 -m is prepared and mixed at room temperature. It is preferred that the silane rate is 0.5-30 % by weight for the solution to be prepared. Afterwards, solvent, acid or base, oxide particles and meltable organic particles are respectively added into the mixture and mixed for a suitable period of time until obtaining a homogeneous mixture. This time period is about one (1) hour. The rate of solvent in the final mixture is preferably 20% by weight.
  • composition used as meltable filling material which has been developed within the scope of the invention is applied on tile surfaces at a suitable temperature by means of pouring or spraying method, and in the surfaces where application is performed; the coating is made to penetrate into pores on the surface by means of mechanical force.
  • the suitable temperature for the surfaces on which application will be performed is between 60°C and 90°C.
  • Mechanical force process may include the following; passing the surface to which composition is applied under felt-coated rotary head wheels/brushes; applying the composition by means of a brush such that it will get into the pores on the surface to which application is made; or passing the surface to which composition is applied under a roll.
  • Said mechanical processes are not limited thereto, but different mechanical processes can be performed in order for the composition to penetrate into the pores on the surface, during or after the application of the composition to the surface.
  • the coating/filling material applied on the surface is enabled to penetrate into the pores of different size present on the tile surface by means of mechanical force.
  • the temperature increases to 80-90°C due to the frictional force effect of the process of mechanical application or force on the tile surface. Therefore, the composition is made to fill into the pores by being completely melted thanks to the organic particles having been used. No thermal treatment is subsequently applied on the surfaces to which composition is applied.
  • the easy-to-clean property of tile surfaces has been tested according to ISO 10545-14 standard after the coating composition developed within the scope of the invention is applied to tile surfaces.
  • alcohol iodide, chromium oxide green or olive oil stains are dropped on tile surfaces, and after waiting for a while, it has been observed that no stain remains on the surface when washed with water subsequent to the stain test having been performed as per the standard.
  • the surfaces have also been tested for daily stains occurring frequently, e.g. tea, coffee, wine, joint filler stains; observing, when washed with water, that the stains are removed.
  • the pores opened during sintering on porcelain tile surfaces are filled and closed with the meltable filling material according to the invention; thus, the surfaces are made resistant against stains, without becoming dull.
  • Products/surfaces comprising the composition prepared according to the invention is also within the scope of the invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The subject matter of the invention relates to a filling material/coating composition which can penetrate into and fill in the pores on surfaces by melting upon being applied on porous surfaces, e.g. on the surfaces of the tiles and to a method developed for preparing and applying said coating/filling material to surfaces and products/surfaces comprising the composition prepared according to the invention. The composition developed within the scope of the invention comprises at least one silane having the general formula of [R (CH2)n]mSi(OR')4-m, at least one silane having the general formula of Si(OR")4, at least one acid or base for the hydrolysis of silanes, a suitable solvent, organic particles and inorganic particles. The composition having been developed is applied to surfaces with suitable temperatures and fills in the pores on said surfaces, as well as reducing stain holding property of the surfaces, thereby making the surfaces easy to clean.

Description

DESCRIPTION
A COATING COMPOSITION DEVELOPED FOR POROUS SURFACES AND A METHOD FOR PREPARING AND APPLYING THIS COMPOSITION TO SURFACES Subject of the Invention
The subject matter of the invention relates to a filling material/coating composition which can penetrate into and fill in the pores on surfaces by melting upon being applied on porous surfaces, e.g. on the surfaces of the tiles and to a method developed for preparing and applying said coating/filling material to surfaces and products/surfaces comprising the composition prepared according to the invention.
State of the Art
Tile is a floor covering material which is commonly used in public and private living spaces, e.g. schools, hospitals, shopping malls, restaurants, kitchens, and bathrooms. It becomes challenging and demanding to clean the stains accumulated on the surface during use as a result of the fact that closed pores therein are opened during polishing processes performed in polished tiles subsequent to production in order to improve the aesthetic appearance. Porcelain tiles have water absorption value less than 0.5% and can be produced by surface embossing, either glazed or unglazed, and they may be defined as white ceramic tiles, or colorful ceramic tiles by the addition of color pigments in starting compositions. Porcelain tiles, due to the low water absorption value and highly vitrified structure thereof, are produced at higher temperatures (1200-1220°C) in longer time periods (50-60 minutes) when compared to floor tiles [Biffi, G., Porcelain stoneware - production manual and methods of use, Gruppo Editoriale Faenza Editrice S.p.A., Faenza, 1999].
Polished porcelain tiles are the most outstanding ones among porcelain tile types. Polished porcelain tiles have brighter and smoother surfaces than unpolished porcelain tiles; however, the former are significantly poor in wearing and staining resistance (i.e. being stainproof) due to the formation of surface cracks and opening of the closed pores during polishing process [Esposito L, The Reliability of Polished Porcelain Stoware TilesJ. Eur. Cer.Soc.25 (2005) 1487-1498].
Today, in order to solve the mentioned problem, hydrophobic/oleophobic surface coatings, which make the surface to which they are applied easier to clean are widely used.
Such materials provide the surfaces to which they are applied with advantages and properties as follows; delay in becoming dirty, being easy to clean, self-cleaning, reducing water and detergent consumption.
The expected properties from such surfaces are follows; not comprising fluorine, i.e. being environmentally friendly, being long-lasting, being easy to be industrially applicable , and having self-cleaning property. Therefore, a need exists for coatings which are environmentally friendly, as well as being easy to clean, long-lasting, hydrophobic, and dirt repellent.
That a surface is easy to clean depends on the chemical composition and micro structure of the related surface. The surfaces that are easy to clean are obtained by performing coating with materials with low surface energy, or by improving surface roughness.
Closed pores of different sizes are formed on the surfaces of the polished porcelain tiles during sintering. In order for the surface to look bright, tile surface is polished using SiC abrasives at the end of firing process. Polishing process causes the surface to hold stains during use since it causes closed pores of 10-50 microns diameter to be exposed. In the present state of the art, the primary method used for increasing staining resistance of the opened pores on the surfaces of the porcelain tiles is the one where wax or silicone type constituents are used in a way to allow film formation on the surface in order for the related surface to be provided with water repellent property. Apart from that, Teflon particles and the mixtures of oxide constituents are widely used for filling the pores. However, wax or silicone type constituents used in the present state of the art cover the surfaces with a thin film, rather than filling the pores on the surface, and although they increase staining resistance at first, they are subject to mechanical weathering in the course of time, and thus losing their characteristics. Another method, forming filling materials using teflon particles, poses a risk for the environment and human . health.
The coating carried out in a way to form a thin film on the tile surface is subject to abrasion after some time, and so its protective effect is lost. Further, since the material remaining on the surface as a film causes surface roughness, the porcelain tiles, which are otherwise expected to have high brightness value, look dull. It is required to rub down the tile to which protective coating is applied having been delivered to the user by using sponge and detergent in order to prevent this appearance. This additional application is not preferred by the user, and also it increases financial losses.
One of the most important deficiencies regarding the protective material mixtures used in the industry for this purpose is that the agents comprised therein are inflammable and hazardous to the environment, in addition to having low chemical and mechanical resistance. Hence, filling materials which fill in the pores upon melting, rather than coatings, are needed in order to prevent such surfaces from getting dirty. The composition having been developed in the present work, said composition filling in the pores upon melting, is filled only into the pores, thereby allowing the surface to preserve the bright appearance thereof. Moreover, the filling material developed within the scope of the invention is an environmentally friendly composition having good chemical and mechanical resistance thanks to the preparation technique and application method thereof.
Some of the compositions and methods developed for increasing the resistance of the surfaces against dirt/stain formation within the present state of the art are given below. The Patent No. DE102007033398, the resistance is increased by filling the pores on porcelain surfaces with particles comprising fluorosilane and silica addition; however, the composition has a surface dulling effect. (Nanocare). In the Patent No. DE10346018A1, a filling material has been developed using fluorine- based silane and some particles; wherein it increases the staining resistance of the surface to which it is applied while reducing the brightness. (Nanoquadrat).
In the Patent No. US7683123B2, on the other hand, a water-based emulsion solution which prevents stain holding and comprises silica has been developed. With the solution having been developed herein, various surfaces (porcelain tile, glass, metal, concrete, etc.) are coated; however, said solution forms a thin film on the surface, rather than penetrating into the pores. Therefore, staining resistance decreases when the coating wears down after some time (Dow Corning).
The Patent Document No. JP2001294778 discloses a coating which can be applied on the surface as a film and is capable of increasing staining resistance of the surfaces. The composition is known to comprise at least one of the following; colloidal silica, sodium silicate (water glass), and additionally a sodium salt, potassium salt, carbonate or bicarbonate group compounds. It has been stated that said compounds may preferably be Na2C03, K2C03, NaCI, KCI, KHC03, Na2S04 and sodium polyphosphate. It has also been pointed out that aluminum silicate, for example, may be used as the compound with aluminum compound. The Patent Documents No. JP2003183581 and JP2005029702 disclose a coating that forms a film on the surface; wherein the composition has the compound with the following formula and X group comprises an alkyl group including amino group, amino alkyl group, vinyl group, epoxy group, glycidoxy group, acrylic group, methacrylic group or sulfhydryl group, but particularly is an amino group. It has been stated that Rl, R2, and R3 groups may be an alkoxy, aryloxy, allyloxy, and halogen group, in addition to OH group, and they may be selected from the groups capable of forming cylanol.
Figure imgf000006_0001
The Patent Document No. CN102561627 discloses a tile having a protecting layer and a layer comprising photocatalyst. It has been stated herein that a coating comprising a protecting layer and Ti02, the photocatalyst, thereon is applied on the tile. What has also been disclosed herein is that a thin film layer is formed on the tile surface subsequent to applying the coating comprising photocatalyst on the tile by spraying method; that oil stains, bacteria, and such factors are removed from the surface thanks to the oxygen and oxyhydrogen radicals formed on the surface due to the sunlight; and that dirt and dusts are prevented from adhering onto the surface.
The Patent Document No. KR20090063322 discloses a new floor tile with increased surface resistance against stains thanks to the transparent film layer formed on the surface. The Patent Document No. JP2002355917 discloses that a composition comprising titanium oxide and tin oxide with photocatalytic property is applied on a surface, for example a tile surface, and thus the stains are prevented from accumulating on the surface. Again, the Patent Document No. JP2001031483 points out that a coating with photocatalytic property comprising Ti02 sol, Si02 sol and peroxotitanic acid is applied on the surface in a way to form a film thereon.
The permanence of easy-to-clean property of all the existing commercial solutions decreases in the course of time when tested in different environments due to the fact that they are applied on the surface as a film. In addition, in the mentioned solutions, easy-to-clean property is provided by using fluorine and flammable solvents, e.g. pentane, are additionally preferred. The developed protecting coatings reduce the brightness of the surface to which they are applied, and so they cannot yield the expected brightness value from the polished porcelain tile surfaces.
Within the composition suggested in the present invention, a filling material which is permanent and environmentally friendly, has high staining resistance, and penetrates into the pores on the surface upon melting and fills in the pores, has been developed. Another advantage provided by the invention is that the tile surfaces maintain their brightness after the polishing process. Since the composition according to the invention does not cause film formation on the surface to which it is applied, it does not have the disadvantages of wearing down and dull appearance of the surface, which are encountered within the present state of the art. OBJECT OF THE INVENTION
The object of the invention is to develop a coating composition to serve as a filling material which will be applied on porous surfaces and is capable of filling/penetrating in the pores upon melting. Another object of the invention is to develop a coating composition which is stable, long-lasting, and easy to apply and has high mechanical and chemical resistance.
Another object of the invention is to develop an environmentally friendly coating composition where silane compounds with no fluorine content are used.
Yet another object of the invention is to develop a coating composition which can become hard on the surface to which it is applied, without requiring any thermal treatment. And another object of the invention is to develop a coating composition which does not damage surface brightness on the surface to which it is applied, is easy to clean, and maintains the brightness value of the surface. DESCRIPTION OF THE INVENTION
The subject matter of the invention relates to a filling material/coating composition which can penetrate into and fill in the pores on surfaces by melting upon being applied on porous surfaces, e.g. on the surfaces of the tiles and to a method developed for preparing and applying said coating/filling material to surfaces and products/surfaces comprising the composition prepared according to the invention.
Closed pores of different sizes are formed on the surfaces of the polished porcelain tiles during sintering thereof. In order for the surface to look bright, tile surface is polished using SiC abrasives at the end of firing process. Polishing process causes the surface to hold stains during use since polishing process causes closed pores of 10-50 microns diameter to be exposed. The coating/filling composition according to the invention is developed for preventing the tile surfaces from holding stains and allowing them to be easy to clean. The composition developed according to the invention closes the pores by filling in/penetrating into them, said pores being opened during sintering, after being applied on the surface upon melting; thus, it prevents the surface from holding the stains, at the same time enabling the surface to be easy to clean.
The easy-to-clean property of tile surfaces has been analyzed in detail within the scope of the invention depending on the source and concentration of the silane compounds forming the coating/filling material applied on the surface; the source, amount, and particle size of the inorganic particles used in the composition; the source, amount, and particle size of meltable organic particles added into the composition; the amount of water required for hydrolysis in the medium; the duration of hydrolysis- condensation; and on solvent to be used. The easy-to-clean property of tile surfaces where the composition developed within the scope of the invention is applied has been tested according to ISO 10545-14 standard.
The composition according to the invention mainly comprises at least one silane or mixtures thereof formulas of which have been stated below, at least one type of oxide particle/inorganic particle, and at least one type of organic particle, the general formulas of which have been given below. Additionally, it comprises at least one acid or at least one base which are used for the hydrolysis of silanes and suitable solvent or solvent mixture.
Functional silanes are used while preparing the coating solution according to the invention. The composition developed within the scope of the invention comprises at least one silane having the general formula of [R (CH2)n]mSi(OR')4-m
The value range of m = ί— 3, and of n = 1 - 24 within the formula. R group may be alkyl, aryl groups; besides, it may be a functional group comprising epoxy or a functional group comprising double bond of polymerizable methacrylate. Moreover, it may also be acid anhydride, acid halide; amino, hydroxy, mercapto, and isocyano- groups. However, the use of alkyls is preferred most of the time.
R' group in the formula may be alkyl, aryl, alkoxy alkyl, or alkoxy aryl groups.
Particularly, the use of silanes comprising methyl, ethyl, and propyl is preferred. Within the scope of the invention, the compounds having the above general formula and/or mixtures thereof may be used as functional silane in the composition.
The coating composition according to the invention comprises at least one silane having the formula below as tetrafunctional silane, in addition to above mentioned silane compound.
Si(OR") R" group in the formula may be alkyl or aryl groups, wherein the use of alkyls, for example methyl, ethyl, propyl, is particularly preferred. The compounds having the general formula of Si(OR")4 and/or mixtures thereof may be used as tetrafunctional silane in the composition:
The composition developed within the scope of the invention comprises at least one silane having the general formula of [R (CH2)n]mSi(OR')4.m and at least one silane having the general formula of Si(OR")4; besides, it may comprise the mixtures of these silanes in different rates. The composition prepared within the scope of the invention comprises 30% silane by weight.
Within the scope of the invention, the compounds such as tetraethyl orthosilicate (tetraethoxysilane), tetramethyl orthosilicate (tetramethoxysilane) and/or the mixtures thereof may be used as the compound having the general formula of Si(OR")4, but tetraethyl orthosilicate (tetraethoxysilane) is preferably used; moreover, the silane compound having the general formula of [R (CH2)n]mSi(OR') .m can be selected from methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octadecyltrimethoxysilane, and hexadecyltrimethoxysilane compounds, but hexadecyltrimethoxysilane is preferably used.
The coating composition developed within the scope of the invention comprises oxide particles/inorganic particles, the particle sizes of which are between 1 and 10 μ such that the amounts thereof, in the final mixture will be between 30 and 40% by weight in order for their surfaces to be modified with silanes, in addition to the silanes. Within the scope of the invention, the use of Si02, Zr02, Al203 and such particles is preferred. For the Si02, one of the oxide particles, the commercially available products Sikron SF300, SF600, SF800 are preferably used. A single type of inorganic particles can be added into the composition; besides, in the form of mixtures of more than one type of inorganic particles can be used in the composition. The composition developed within the scope of the invention comprises organic particles that provide the material with melting property. The size of the particles to be used is in compliance with that of the pores on the tile surface and the surface where application will be performed. Hydrocarbon wax particles are mostly preferred. It is also possible to use polyethylene or polypropylene wax or teflon (PTFE) or the mixtures thereof within the scope of the invention. The organic particles used within the scope of the invention may be hydrocarbon wax in the form of dispersion and/or in granule form that can melt while being applied on tile surface; likewise, the use of poly tetra fluoro ethylene (PTFE, teflon) modified hydrocarbon wax particles, i.e. particles comprising a layer of PTFE on the surface thereof, is also possible. In the composition according to the invention, a single type of organic particles can be used; likewise, it is possible to use the mixture of more than one organic particles. The organic particles added in the composition are done so such that their rates will be 30-40% by weight in the final solid. The organic particles to be used are selected from the products with the trade names DEUTERON-WAX MPO (micronized polyolefin wax), DEUTERON-WAX PP (micronized polypropylene wax), DEUTERON-WAX TF (micronized PTFE-modified polyolefin wax) DEUTERON MM 823 (PTFE-modified micronized plastic), Licolub H4 (Modified hydrocarbon wax), Ceridust 3610 (high density PE), Licocene PP 1302 TP (PP granules, fine grain), Licocene PP 6102 (PP granules, fine grain), Licocene PP 7502 TP (PP granules, fine grain), Ceridust 3831 (Modified polyethylene wax), Ceridust 3920 F (PTFE modified polyethylene wax), Ceridust 9202 F (Polytetrafluoroethylene), MICHEM EMULSION 11226 (Cationic PP emulsion), MICHEM EMULSION 36840A (Anionic parafin/PE wax emulsion), MICHEM EMULSION 61840A (Nonionic PP wax emulsion), MICHEM EMULSION 66035 (Anionic parafin/PE wax emulsion), MICHEM EMULSION 91735 (Nonionic PP emulsion), Luba print 539 (Parafin wax), Luba print 459 (Parafin wax), Luba print 760/D (PE wax), Luba print 445/B (Parafin wax), Luba print 942/P (PE wax), Luba print T-152/D30 (PE wax), Luba print 280/F (Parafin wax).
In the composition developed within the scope of the invention, alcohol, ethanol, propanol, isopropanol, tertiary butanol, l-methoxy-2-propanol, 2-butoxyethanol, 1- propoxy propanol, 2-ethyl hexanol, diacetone alcohol and/or mixtures thereof, particularly isopropanol or 1-propoxy propanol or the mixture of isopropanol and 1- propoxy propanol can be' used as solvent. The composition comprises 20% solvent by weight.
The hydrolysis of the silanes used in the composition during the preparation of the composition developed within the scope of the invention is performed at different pH values. To that end, hydrochloric acid, phosphoric acid, nitric acid, sulphuric acid, acetic acid, propanoic acid, maleic acid, carbonic acid, citric acid can be used as acid while sodium hydroxide, sodium carbonate, potassium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine can be used as base. The composition comprises at least one acid or base. Acid or base can be added into the mixture in the amount of 1/100 moles of silicium in the silane compound added into the composition.
In order to prepare the composition developed within the scope of the invention, a solution comprising 0.1-50% by weight of at least one type of silane compound having the general formula of Si(OR")4 and at least one silane compound having the general formula of R(CH2)n]mSi(OR')4-m is prepared and mixed at room temperature. It is preferred that the silane rate is 0.5-30 % by weight for the solution to be prepared. Afterwards, solvent, acid or base, oxide particles and meltable organic particles are respectively added into the mixture and mixed for a suitable period of time until obtaining a homogeneous mixture. This time period is about one (1) hour. The rate of solvent in the final mixture is preferably 20% by weight.
The composition used as meltable filling material which has been developed within the scope of the invention is applied on tile surfaces at a suitable temperature by means of pouring or spraying method, and in the surfaces where application is performed; the coating is made to penetrate into pores on the surface by means of mechanical force. The suitable temperature for the surfaces on which application will be performed is between 60°C and 90°C. Mechanical force process may include the following; passing the surface to which composition is applied under felt-coated rotary head wheels/brushes; applying the composition by means of a brush such that it will get into the pores on the surface to which application is made; or passing the surface to which composition is applied under a roll. Said mechanical processes are not limited thereto, but different mechanical processes can be performed in order for the composition to penetrate into the pores on the surface, during or after the application of the composition to the surface. Thus, the coating/filling material applied on the surface is enabled to penetrate into the pores of different size present on the tile surface by means of mechanical force. The temperature increases to 80-90°C due to the frictional force effect of the process of mechanical application or force on the tile surface. Therefore, the composition is made to fill into the pores by being completely melted thanks to the organic particles having been used. No thermal treatment is subsequently applied on the surfaces to which composition is applied.
The easy-to-clean property of tile surfaces has been tested according to ISO 10545-14 standard after the coating composition developed within the scope of the invention is applied to tile surfaces. In the present study, alcohol iodide, chromium oxide green or olive oil stains are dropped on tile surfaces, and after waiting for a while, it has been observed that no stain remains on the surface when washed with water subsequent to the stain test having been performed as per the standard. Moreover, the surfaces have also been tested for daily stains occurring frequently, e.g. tea, coffee, wine, joint filler stains; observing, when washed with water, that the stains are removed. Thanks to the composition developed within the scope of the invention, the pores opened during sintering on porcelain tile surfaces are filled and closed with the meltable filling material according to the invention; thus, the surfaces are made resistant against stains, without becoming dull. Products/surfaces comprising the composition prepared according to the invention is also within the scope of the invention.

Claims

A coating composition serving as a filling material which can be applied on porous surfaces and fill in/penetrating into the pores on the surface, characterized in comprising; at least one type of silane having the general formula of [R (CH2)n]mSi(OR')4-m/ at least one type of silane having the general formula of Si(OR")4,
at least one type of organic particle, and
at least one type of inorganic particle.
The composition according to Claim 1, characterized in that it further comprises;
• at least one type of solvent, and
• at least one type of acid or at least one type of base for the hydrolysis of silanes.
The composition according to Claim 1, characterized in that it comprises silane group compounds in the amount of 30% by weight.
The composition according to Claim 2, characterized in that the used solvent is at least one of, or the mixtures of, alcohol, ethanol, propanol, isopropanol, tertiary butanol, l-methoxy-2-propanol, 2-butoxyethanol, 1-propoxy propanol, 2-ethyl hexanol and diacetone alcohol.
The composition according to Claim 4, characterized in that the used solvent is isopropanol or 1-propoxy propanol or a mixture of isopropanol and 1-propoxy propanol.
The composition according to Claim 5, characterized in that it comprises the solvent in the amount of 20% by weight.
7. The composition according to Claim 2, characterized in that the used acid is an acid selected from hydrochloric acid, phosphoric acid, nitric acid, sulphuric acid, acetic acid, propanoic acid, maleic acid, carbonic acid, and citric acid.
8. The composition according to Claim 2, characterized in that the used base is a base selected from sodium hydroxide, sodium carbonate, potassium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, and tributylamine.
9. The composition according to Claims 7 and 8, characterized in that it comprises said acid or base in the amount of 1/100 moles of the the silicium in the silane compound added into the composition.
10. The composition according to Claim 1, characterized in that the "m" value is between 1 and 3 and "n" value is between 1 and 24 within the compound having the general formula of [R (CH2)n]mSi(OR')4-m.
11. The composition according to Claim 10, characterized in that R' group is at least one of alkyl, aryl, alkoxy alkyl or alkoxy aryl groups.
12. The composition according to Claim 10, characterized in that R group is at least one of alkyl, aryl, epoxy group or a functional group comprising double bond of polymerizable methacrylate or one of acid anhydride, acid halide, amino, hydroxy, mercapto and isocyano groups.
13. The composition according to Claim 11, characterized in that (R') group may be alkyl group and particularly selected from methyl, ethyl or propyl.
14. The composition according to Claim 1, characterized in that the (R") group mentioned in the general formula of Si(OR")4 is one of alkyl or aryl group.
15. The composition according to Claim 14, characterized in that the (R") group mentioned in the general formula of Si(OR")4 is one of methyl, ethyl and propyl groups.
16. The composition according to Claim 15, characterized in that the compound having the general formula of Si(OR")4 is at least one of and/or the mixtures of the compounds including tetraethyl orthosilicate (tetraethoxysilane) and tetramethyl orthosilicate (tetramethoxysilane).
17. The composition according to Claim 13, characterized in that the compound having the general formula of [R (CH2)n]mSi(OR')4.m is at least one of, or the mixtures of, the compounds of methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octadecyltrimethoxysilane, and hexadecyltrimethoxysilane.
18. The composition according to Claim 16, characterized in that the compound having the general formula of Si(OR")4 is tetraethyl orthosilicate (tetraethoxysilane).
19. The composition according to Claim 17, characterized in that the compound having the general formula of [R (CH2)n]mSi(OR') -m is hexadecyltrimethoxysilane.
20. The composition according to Claim 1, characterized in that the used organic particles are hydrocarbon wax particles or teflon, or the mixtures thereof; and that the sizes of the particles are such that they will be compatible with the pore size on the surface where composition will be applied.
21. The composition according to Claim 20, characterized in that the used hydrocarbon wax particles is at least one of, or the mixture of, polyethylene wax and polypropylene wax.
22. The composition according to Claim 21, characterized in that the used hydrocarbon wax particles are hydrocarbon waxes in granule form and/or dispersion form, or teflon modified hydrocarbon waxes.
23. The composition according to Claim 22, characterized in that the used organic particles are comprised such that their amounts will be 30-40% by weight in the final solid.
24. The composition according to Claim 1, characterized in that said inorganic particles are oxide particles, preferably at least one of, or the mixture of, Si02, Zr02, Al203 particles.
25. The composition according to Claim 24, characterized in that the size of the inorganic particles comprised therein is between 1 and 10μ.
26. The composition according to Claim 24, characterized in that the used inorganic particles are comprised such that their amounts will be 30-40% by weight in the final mixture.
27. A method for preparing the composition mentioned in the preceding claims, characterized in comprising the process steps of;
• preparing a solution comprising at least one type of silane compound having the general formula of Si(OR") and at least one silane compound having the general formula of R(CH2)n]mSi(OR')4-m in the amount of 0.1-50% by weight
• mixing the resulting solution at room temperature, and • adding solvent, acid or base, inorganic/oxide particles and meltable organic particles respectively into the resulting mixture and mixing the same for a suitable period of time until obtaining a homogeneous mixture.
28. The method according to Claim 27, characterized in that the silane amount is 0.5-30% by weight in the prepared solution.
29. The method according to Claim 27, characterized in that the mixture is mixed for one (1) hour until obtaining a homogeneous mixture.
30. The method according to Claim 27, characterized in that the solvent is added into the solution such that its amount will be 20% by weight of the final mixture.
31. The method according to Claim 27, characterized in that inorganic particles are added into the solution such that their amount will be 30-40% by weight of the final mixture.
32. The method according to Claim 27, characterized in that organic particles are added into the solution such that their amount will be 30-40% by weight of the final mixture.
33. The method according to Claim 27, characterized in that the acid or base is added into the composition in the amount of 1/100 moles of silicium in the silane compound added into the composition.
34. The method according to Claim 27, characterized in that the solvent added into the composition is at least one of, or the mixtures of, alcohol, ethanol, propanol, isopropanol, tertiary butanol, l-methoxy-2-propanol, 2- butoxyethanol, 1-propoxy propanol, 2-ethyl hexanol, and diacetone alcohol.
35. The method according to Claim 34, characterized in that the solvent added into the composition is isopropanol or 1-propoxy propanol or a mixture of isopropanol and 1-propoxy propanol.
36. The method according to Claim 27, characterized in that the used acid is selected from hydrochloric acid, phosphoric acid, nitric acid, sulphuric acid, acetic acid, propanoic acid, maleic acid, carbonic acid, and citric acid.
37. The method according to Claim 27, characterized in that the used base is selected from sodium hydroxide, sodium carbonate, potassium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, and tributylamine.
38. The method according to Claim 27, characterized in that the used organic particle is at least one of, or the mixture of, polyethylene wax, polypropylene wax, teflon, teflon modified polyethylene wax, and teflon modified polypropylene wax.
39. The method according to Claim 27, characterized in that the used inorganic particles are oxide particles, preferably at least one of, or the mixture of, Si02, Zr02, Al203 particles.
40. The method according to Claim 27, characterized in that the compound added into the composition and having the general formula of Si(ORM) is at least one of and/or the mixtures of the compounds including tetraethyl orthosilicate (tetraethoxysilane), and tetramethyl orthosilicate (tetramethoxysilane).
41. The method according to Claim 39, characterized in that the compound added into the composition and having the general formula of Si(OR")4 is tetraethyl orthosilicate (tetraethoxysilane).
42. The method according to Claim 27, characterized in that the compound added into the composition and having the general formula of [R (CH2)n]mSi(OR')4-m is at least one of, or the mixtures of, the compounds of methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octadecyltrimethoxysilane, and hexadecyltrimethoxysilane.
43. The method according to Claim 41, characterized in that the compound added into the composition and having the general formula of [R (CH2)n]mSi(OR')4-m is hexadecyltrimethoxysilane.
44. A method fo applying the composition to mentioned in the preceding claims, characterized in comprising the process steps of;
• applying the composition on surfaces having suitable temperature by means of pouring or spraying method,
• allowing the composition to fill into the pores on the surfaces by mechanical force
• increasing the temperature of the surface to which application is made to 80- 90°C with the frictional force effect due to mechanical force, and filling/penetrating the composition into the pores of different size on the surface upon melting.
45. The method according to Claim 43, characterized in that the surfaces to which composition is applied have a temperature between 60°C and 90°C.
46. The method according to Claim 43, characterized in that said mechanical force process includes passing the surface to which composition is applied under brush, rotary head wheel or roll; or spreading the composition onto the surface by means of a brush.
47. The method according to Claim 43, characterized in that the composition gets into the pores present on the surface by melting and thus fills/penetrates into the pores.
48. Product/surface comprising the composition prepared according
preceding claims.
PCT/TR2014/000511 2014-01-22 2014-12-26 A coating composition developed for porous surfaces and a method for preparing and applying this composition to surfaces WO2015112101A1 (en)

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WO2017082837A1 (en) * 2015-11-12 2017-05-18 Toyota Boshoku Türki̇ye Otomoti̇v Sanayi̇ Ve Ti̇c. A. Ş. Non-stick coating material applied to mold to prevent sticking of material produced in metal surface production molds
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