KR100934498B1 - Liquid non-slip agent using uniform patterned etching surface - Google Patents

Abstract

PURPOSE: A liquid anti-slip agent is provided to impart fast reaction and consistency during an etching reaction, to prevent the liquid from being distributed during spray coating, and to suppress uneven reaction by moisture evaporation. CONSTITUTION: A liquid anti-slip agent for inorganic tile etching comprises an etchant 1.0~5.0 weight%, a PH adjusting agent 0.1~10.0 weight%, a moisture-holding agent 0.01~2.0 weight%, a non-ionic surfactant 0.01~5.0 weight%, an indicator 0.01~5.0 weight%, and the balance of water. The etching agent is NH4HF. The pH adjusting agent is any one or at least two selected from phosphoric acid(H3PO4), hydrofluoric acid(HF), sulfuric acid(H2SO4), hydrochloric acid(HCl), acetic acid(CH3COOH) or polyphosphate.

Description

Liquid Non-slip Agent Using Uniform Patterned Etching Surface}

The present invention relates to a liquid composition capable of visually identifying the reaction completion state in the construction of the anti-slip agent by imparting a discoloration function according to the hydrogen ion index (pH).

The present invention relates to a liquid composition capable of visually identifying the reaction completion state in the construction of the anti-slip agent by imparting a discoloration function according to the hydrogen ion index (pH). More specifically, it is based on ammonium fluoride (NH ₄ F.HF), and pH adjusting agent such as polyphosphoric acid (H _{n + 2} P _n O _{3n + 1} , n = 1 to 2) as a pH adjusting agent of the composition, In the non-slip composition comprising a color retaining agent, such as a surfactant and methyl orange (or methyl red, bromcresol green, etc.) to increase the wetting effect of the wetting agent and the treated surface in order to increase the wetness sustainability. It relates to a manufacturing method.

The present invention forms a micropore of a uniform pattern by etching a surface of an inorganic material such as a tile or a natural marble made of a finishing agent on the bottom surface of a bathroom, a public bath, and an indoor / outdoor swimming pool to prevent slippage by removing water film from the surface. It relates to a method for preparing a composition of the liquid anti-slip agent to maximize the effect.

Up to now, inorganic materials such as tiles and marbles have been constructed on the floors of places where water is essential, such as bathrooms, public baths, and swimming pools, for water leakage and aesthetics of the interior. These materials have good durability, abrasion resistance, water resistance and discoloration, and their usage is essential in the construction industry. However, most of the inorganic flooring materials such as tiles and marbles are very smooth materials with high smoothness and gloss characteristics. Therefore, where water and soap are essential, the friction coefficient is low due to water film phenomenon. There is no fear that fractures and transcription accidents occur frequently.

In order to solve this problem, there is a manufacturing method of floor tiles having the surface unevenly formed by etching in the manufacturing process of the inorganic flooring material (tile) and finally coating the surface with a polishing agent (Korean Utility Model Publication No. 20-0375692). It can be used only for the application of new buildings, and the anti-slip effect due to the final gloss treatment is relatively low.

In addition, recently, various anti-slip agents have been developed and sold to minimize the water film phenomenon, which is the root cause of slipping, by applying a chemical treatment agent that can cause reaction with surface components of the inorganic floor material to the inorganic floor material to form fine irregularities on the surface. It is becoming.

The anti-slip agent for mitigating the surface of the inorganic flooring material is composed mainly of fluorine salts such as aqueous hydrogen fluoride solution and ammonia bifluoride, and is composed of aliphatic carbonates and surfactants (Korea 1993-0023310) and polyethylene glycol or In order to add antibacterial properties to the composition (Japan Patent No. 2000-0248262) and the composition to which ammonium hydroxide was added as a reaction control agent (Korea Republic 2008-0011255) with the addition of ether-based hydrophilic solvent to enhance the wetting, penetration, and dispersing action. An anti-slip composition (Korea 2008-0011256), etc., characterized in that it further comprises silver nanoparticles.

According to the material and composition of the flooring material, the composition of the aqueous solution to mitigate the slip of the surface of the inorganic flooring material is used by the user of the anti-slip agent to determine the approximate delay time for the completion of an appropriate reaction during the treatment of the inorganic flooring material. The response time is also different, which makes it difficult to determine the proper treatment status. In addition, for a long time for sufficient surface treatment, the applied anti-slip agent solution evaporated rapidly from the surface of the flooring material, there was a fear of aesthetic damage due to stain or whitening phenomenon due to the non-uniform reaction of each part.

Due to such instability of the prior art, the development of a product that enables the control of the reaction rate by adding various additives has been made, but it is considered that there is a limit in arbitrarily judging the completion of the surface reaction according to the countless types of flooring materials.

Therefore, in the present invention, ammonium bifluoride (NH ₄ F.HF) is a basic component to supplement the conventional technology, and polyphosphoric acid (H _{n + 2} P _n O _{3n + 1} , n = 1 In preparing an anti-slip agent composition solution having an appropriate ratio by adding an acid component such as ˜2), etching is performed due to a chemical reaction on the surface of the inorganic floor covering.

Therefore, in the initial acidic solution, salts may be generated by the neutralization reaction with the inorganic components on the surface of the flooring material, and the change to the neutral solution (pH 7) may be gradually achieved. In addition, the present invention, by adding a wetting agent such as a water-soluble polymer such as hydroxyethyl cellulose (HEC) in order to increase the sustainability of the wet, so that the solution can be applied evenly without scattering when applied to the tile by a method such as spraying In order to make uniform etching, add a surfactant to increase the uniform wetting effect of the treated surface, and change color indicator such as methyl orange (or methyl red, bromcresol green, etc.). Including the neutralization reaction according to the progress of etching on the surface of the inorganic flooring material, including the color change as the pH of the coating liquid is changed from acidic to neutral, for anyone to easily prepare a non-slip composition for the non-slip treatment will be.

In order to achieve the above object, the present invention provides a water-soluble slipper, including an ammonium bifluoride, a pH adjusting agent, a wetting agent, a wettability enhancer and a color change reagent in a water-soluble slipper.

According to the present invention, the color of the etchant changes as the surface of the inorganic flooring agent is etched to indicate the completion point of the etching, thereby visually confirming that there is a poor performance or incomplete etching surface due to incomplete etching. There is an advantage to stop.

More specifically, as an example of the present invention, the anti-slip compositions include amnonium bifluoride, polyphosphoric acid, hydroxyethyl cellulose, surfactants and methyl oranges (methyl red, bromcresol green, thymol blue, brothymol blue, cresol red). And a color change reagent such as alizarin yellow, alkali blue, phenolphthalein, and the like.

Hereinafter will be described in more detail with respect to the present invention.

In the aqueous solution of amnonnium bifluoride which is the main component of the liquid antislip agent of the present invention, an acid component which is mixed with ammonium bifluoride as a pH adjusting agent and adjusts the pH is added. By this mixing, when the non-slip agent is applied to the surface of the flooring material, it adds rapid reaction and persistence in the process of etching reaction on the surface of the flooring material, and prevents uneven reaction by moisture evaporation of the applied composition liquid, thereby uniformizing the surface of the inorganic flooring material. The pattern is formed to act. The pH adjuster of the present invention is a weak acidity of less than pH 4 of an aqueous solution such as polyphosphoric acid, phosphoric acid (H ₃ PO ₄ ), hydrofluoric acid (HF), sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), acetic acid (CH ₃ COOH) It can be adjusted by solution. In the present invention, the polyphosphoric acid was mainly used, but even when the acid other than poly was used, the effect was not different from the polyphosphoric acid.

In the present invention, the wetting and maintaining agent plays a role in maintaining the moisture and preventing the hydroxymethyl cellulose (HMC), hydroxyethyl cellulose (HEC), hydroxypropyl methyl cellulose (HPMC), carboxymethyl cellulose (CMC Water-soluble natural and synthetic polymers such as polyvinyl alcohol (PVA), polyacrylic acid, polyacrylamide, polyvinylpyrrolidone and casein can be used. Among them, hydroxyethyl cellulose is preferred. The wetting and maintenance agent of the present invention prevents the non-uniform reaction of the anti-slip agent solution applied to the surface of the inorganic flooring material from the evaporation of water and at the same time prevents the liquid from being scattered during the application to the flooring material in the form of a spray Play a role, allowing more stable use.

 Next, the surfactant is used to increase the uniform wetting effect on the surface during the application to the inorganic flooring material of the anti-slip agent. Anionic (-), cationic (+), zwitterionic (+,-) and nonionic surfactants can be used as the types used, but relatively less bubbles (bubbles) are generated and solubility in all pH ranges. It is preferable to use a good nonionic surfactant, and the kind thereof is not particularly limited as long as it is a component used as a conventional surfactant, and thus further description is omitted.

In the present invention, in order to easily check the progress of the reaction, a discoloring reagent such as methyl orange, methyl red, bromcresol green, thymol blue, bromothymol blue, cresol red, alizarin yellow, alkali blue, phenolphthalein, etc. may be additionally added. Excess hydrofluoric acid (HF) contained in the ammonium bifluoride, the main component of the anti-slip agent composition, as the anti-slip agent was applied to the inorganic flooring material and the reaction proceeded in the initial acidic solution due to the chemical reaction on the surface. It proceeds to produce salt and water while causing neutralization reaction with inorganic component of (SiO ₂ ). Therefore, the initial pH is gradually increased and the discoloration reagent (methyl orange) in the discoloration range (pH 3.1 ~ 4.4) The discoloration of the color was visually confirmed to make it easy to judge the completion of the reaction. The range of addition of such indicators is preferably 0.01 to 1.0% by weight based on the total composition.

The composition range of the liquid slippering agent has a stability range defined by the friction coefficient measurement values of the US Standard Test Standard (ASTM C 1028-96) and the Occupational Safety and Health Agency (OSHA), as shown in the following examples. At the same time, there is no discoloration due to the uniform reaction on the surface of the inorganic flooring material and has a discoloration function so that anyone can easily determine the treatment time of an appropriate anti-slip effect.

Hydrogen fluoride (HF) and flooring material supersaturated in ammonium bifluoride in the process of adding polyphosphoric acid and an indicator to the surface of the inorganic flooring material as a pH adjuster in an aqueous solution of an antislip agent containing ammonium bifluoride ( SiO _{2 type} ) Etching of the surface and ammonium phosphate salt generated through neutralization reaction, the color change of chemical reaction formula and discoloration reagent as follows changes red color from pH1 ~ 3.1 to pink color from pH3.1 ~ 4.4 When it exceeds 4.4, the color turns yellow and the reaction is completed. Also, the part not etched can be confirmed as the color (see FIG. 1).

      If the aqueous solution of the anti-slip agent is excessively high in ammonium biflohydride, the discoloration reagent may be discolored late and the surface of the floor may be discolored due to excessive etching. It is very important to formulate to have.

      Therefore, the appropriate amount of content is preferably 1.0 to 5.0% by weight, and discoloration occurs rapidly at 1.0% by weight or less, but the increase of the friction coefficient is relatively low, which is not preferable. After the etching process is completed, the surface of the flooring material will cause discoloration (whitening), so it is necessary to tune in the available range.

In order to achieve the stated object of the present invention, in the ammonium bifluoride composition, 0.1 to 10.0% by weight of polyphosphoric acid, 0.01 to 2.0% by weight of hydroxyethyl cellulose, 0.01 to 5.0% by weight of nonionic surfactant and discoloring reagent ( Methyl red, methyl orange, bromcresol and the like) provides a composition of the liquid anti-slip agent further comprises 0.01 to 5.0% by weight.

       On the other hand, the change in pH according to the amount of the ammonium bifluoride and polyphosphoric acid covered in the present invention is shown in Table 1 and Table 2 below. Table 1 shows the acid value (pH) of the aqueous solution containing 0.5 to 5.0% by weight of ammonium bifluoride, and Table 2 measures the adjusted value of pH according to the amount of polyphosphoric acid added to the aqueous solution based on 2.5% by weight of ammonium bifluoride. It is shown.

  Table 1

  Table 2

  As shown in Table 1, the pH change of the solution according to the addition amount of ammonium bifluoride, which is the main raw material of the liquid anti-slip agent, even if the content is increased, the acid value (pH 4.5 ㅁ 0.2) hardly changes, and polyphosphoric acid is added thereto. In this case, it can be easily controlled by the discoloration range of the discoloring reagent (Methyl orange: 3.1 ~ 4.4). Therefore, the pH of the inorganic floor is etched while the ammonium bifluoride reacts with the polyphosphoric acid to neutralize it. As the color of the etching passes pH4.4 and the color changes, the end point of the etching can be known (see FIG. 1).

An object of the present invention further comprises a pH adjusting agent, a wetting agent, a wettability enhancer (surfactant) and a discoloration reagent (indicator, methyl orange) in the water-soluble anti-slip agent composition comprising ammonium bifluoride is carried out the etching reaction It adds fast reaction and persistence in the process, prevents the liquid from being scattered during the process of applying to the surface of the flooring material in the form of a spray of the applied composition liquid, and enables more stable use, and prevents uneven reaction caused by evaporation of water. As a result, a uniform pattern on the surface of the inorganic flooring material was prevented from forming and whitening by whitening.

In addition, by visually confirming that the color of the solution applied to the inorganic flooring material is discolored according to the progress of the surface etching reaction, it is possible to achieve the effect of easily determining the completion of the reaction.

Hereinafter, the present invention will be described with reference to one example for specific description, but the present invention is not limited to the following examples.

(Examples 1 to 6)

As shown in Table 3 below, liquid anti-slip agent compositions having different composition ratios were prepared, and the results according to the respective etchings were compared. Composition and composition ratio of the composition is 2.0 to 3.0% by weight of ammonium bifluoride, 2.0 to 6.0% by weight of polyphosphoric acid, 0.2% by weight of hydroxyethyl cellulose, 0.05% by weight of discoloring reagent (methyl orange and Each was adjusted to include 0.5% by weight of a nonionic surfactant (polyethylene glycol monomethyl ether) After preparing the composition according to each of the examples in Table 3, and then applied to SiO ₂ tiles to etch for 10 minutes, The degree of scattering and the color change of the liquid phase over the reaction time and the progress of the reaction were also compared, and the friction coefficient after completion of the reaction (Korean Industrial Standard KS ISO 10545-17) and ceramic tile fine color difference (Korean Industrial Standard KS ISO 10545-16). ) Was measured and the results are shown in Table 3.

    (Comparative Examples 1 and 2)

Ammonium bifluoride and polyphosphoric acid were prepared without additives in 1.0 and 5.0 wt% of the composition solution, respectively, and applied to SiO ₂ -based tiles.

    Table 3

     As shown in the results of Table 3, in Examples 1 to 6, a new anti-slip composition containing ammonium bifluoride, polyphosphoric acid, hydroxyethyl cellulose, a surfactant, and a color change reagent was sprayed onto the inorganic base material to be etched. In this case, it is possible to prevent scattering during spraying and to maintain the long-term wetness, and to increase the wettability when applying the flooring surface, and through this effect, it can be seen that it has the effect of achieving a uniform pattern surface etching. In addition, according to the above embodiment, as shown in Figure 2 (corresponding to Example 3) the experimental results of the building flooring material using the composition of the present invention, the flooring material after the etching process is clearly produced non-slip pattern is excellent effect It can be seen that, furthermore, the color change color change (Methyl orange) as the reaction proceeds, as shown in Figure 3 is applied to the flooring (tile) and visually confirmed that the color of the composition changes as the reaction proceeds It was possible to manufacture a liquid slipper that anyone can easily confirm the completion of the reaction.

  Comparative Examples 1 and 2 were prepared without the addition of a physical reinforcing material. In Comparative Example 1, the coefficient of friction was less than 0.7, and the anti-slip effect was insufficient. In Comparative Example 2, the surface friction coefficient was high, but after treatment was completed. Excessive etching effect caused discoloration (whitening) of the flooring material, which resulted in undesirable results.

In addition, in the case of Comparative Examples 3 to 4, the etching effect on the foil material was fast due to the inclusion of excessive ammonium bifluoride and polyphosphoric acid, but decolorization (whitening) occurred severely, and the addition amount of hydroxyethyl cellulose used as a humectant was excessive. Because of the high viscosity (100cps or more), the spray was not properly sprayed and the color change of the liquid phase hardly occurred according to the reaction progress.

1 is a view showing a change in color for each pH according to the neutralization reaction,

2 is an electron micrograph of a building flooring tile (SiO ₂ system) surface treated with a liquid slipper (Example 3),

3 is an optical picture showing the color change of the liquid according to the progress of the reaction of the building flooring tile (SiO ₂ system) with the liquid slipper (Example 3).

Claims (5)

Anti-slip agent 1.0 to 5.0% by weight of the total weight of the total composition, 0.1 to 10.0% by weight pH adjuster, 0.01 to 2.0% by weight wetting agent, 0.01 to 5.0% by weight nonionic surfactant, 0.01 to 5.0% by weight discoloring reagent A liquid slipper for inorganic tile etching, the remainder being water. delete The method of claim 1, The etchant is NH ₄ HF, the pH adjusting agent is selected from phosphoric acid (H ₃ PO ₄ ), hydrofluoric acid (HF), sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), acetic acid (CH ₃ COOH) or polyphosphoric acid The liquid slipper, characterized in that any one or two or more components, the acid of the etching solution aqueous solution which can be adjusted to 4 or less. The method of claim 3, wherein       The wetting and maintaining agent is hydroxymethyl cellulose (HMC), hydroxyethyl cellulose (HEC), hydroxypropylmethyl cellulose (HPMC), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polyacrylic acid, polyacrylamide Liquid slipper is one or a mixture of two or more selected from polyvinylpyrrolidone, casein. The method according to any one of claims 1, 3 and 4, The discoloration reagent is a liquid slipper is one or two or more selected from methyl orange or methyl red, bromcresol green, thymol blue, brothymol blue, cresol red, alizarin yellow, alkali blue, phenolphthalein.

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