KR101502035B1 - Water-soluble ceramic paint composition - Google Patents

Abstract

The present invention relates to a water-soluble ceramic paint composition and, more specifically, a water-soluble ceramic binder slurry, which is manufactured by an alumina sol, and a water-soluble ceramic paint composition including the same. In the present invention, provided is a manufacturing method of the water-soluble ceramic binder slurry, which comprises the steps of manufacturing an alumina sol with adjusted pH; adding zirconium compounds to an alumina sol solution and firstly hydrolyzing the same; and consecutively adding diatomite and catalysts to the first hydrolyzed and secondly hydrolyzing the same.

Description

[0001] WATER-SOLUBLE CERAMIC PAINT COMPOSITION [0002]

The present invention relates to an aqueous ceramic coating composition, and more particularly, to an aqueous ceramic binder slurry containing alumina sol and an environmentally friendly aqueous ceramic coating composition containing the slurry.

In general, paints are widely used in various fields such as railway, automobile, ship, road facility, electric and electronic industries, as well as kitchens and living rooms.

These paints can be classified into natural resin paints, organic (synthetic resin) paints, water-based paints and inorganic paints according to the kinds of the contained components. Dryness, gloss, hardness, adhesiveness, The characteristics of the back coat vary. In Korea, organic paints having excellent workability and flexibility are being commercialized.

On the other hand, since organic paints are produced using organic solvents such as alcohols and synthetic resin binders, harmful substances causing environmental pollution are not only essential but also have a problem of releasing a large amount of toxic chemical gases when the coating film is burned.

Recently, in order to solve such problems, studies on environmentally friendly functional paints that can replace organic paints have been actively conducted.

Patent Document 1 describes an inorganic coating composition using a water-soluble silicate and a water-soluble silicate made of aluminum or an aluminum metal oxide as a main material. However, since the water-soluble modified silicate used as the binder is a strong alkaline substance, the coating composition according to the above patent has a problem that a slight amount of alkali component is eluted to the surface of the coating film after the coating film is formed, causing whitening. Moreover, the organic substances in the composition prevent micropores in the coating film, thereby failing to maximize the effect of preventing condensation.

Therefore, it is urgently required to develop a water-based ceramic coating composition which is environment-friendly, has a simple construction, and is excellent in workability and economical efficiency.

Patent Document 1: Korean Patent Publication No. 2000-0002219

SUMMARY OF THE INVENTION Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art,

The present invention provides a method for producing an aqueous ceramic binder slurry.

The present invention also provides an aqueous ceramic coating composition comprising the aqueous ceramic binder slurry prepared by the above method.

In order to achieve the above object, in one embodiment of the present invention

preparing an alumina sol aqueous solution having pH adjusted;

Introducing a zirconium compound into the alumina sol aqueous solution to perform a first hydrolysis reaction; And

And sequentially introducing diatomaceous earth and a catalyst into the resultant product of the first hydrolysis reaction and performing a second hydrolysis reaction. The present invention also provides a method for producing an aqueous ceramic binder slurry.

In another embodiment of the present invention,

The aqueous ceramic binder slurry prepared by the above method,

Optionally at least one additive selected from the group consisting of pigments, alumina, zirconium and fillers.

In the present invention, by using an aqueous solution of alumina sol having a pH controlled at the time of preparing the aqueous ceramic coating composition, the adhesive strength to the base material is improved, and the formation of a coating film or the generation of toxic gas during a fire is reduced. Further, the aqueous ceramic coating composition of the present invention does not block the micropores in the coating film by including the aqueous ceramic binder, thereby maximizing the dew condensation effect and air purification effect.

1 is a test report mark of an aqueous ceramic coating composition prepared according to the present invention.
FIG. 2 is a test report showing data on the incombustibility test and gas toxicity test results of the aqueous ceramic fireproof coating composition prepared according to the present invention. FIG.
Fig. 3 is a test report showing a graph of a nonflammable test result.
4 to 6 are test reports showing graphs of the results of the gas toxicity test.

Hereinafter, a method for producing an aqueous ceramic binder slurry according to preferred embodiments of the present invention and an aqueous ceramic coating composition comprising the aqueous ceramic binder slurry prepared by the method will be described in detail with reference to the following specific examples. It is to be understood that the following description is not intended to limit the scope of the specific embodiments of the present invention but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention. Also, the various components used in the detailed description should not be limited by the terms stated. In addition, terms used in the detailed description have the same meaning as commonly understood by a person having ordinary skill in the art to which the present invention belongs, including technical or scientific terms, unless otherwise defined.

In one embodiment of the invention

preparing an alumina sol aqueous solution having pH adjusted;

Introducing a zirconium compound into the alumina sol aqueous solution to perform a first hydrolysis reaction; And

And sequentially introducing diatomaceous earth and a catalyst into the resultant product of the first hydrolysis reaction and performing a second hydrolysis reaction. The present invention also provides a method for producing an aqueous ceramic binder slurry.

First, in the method of the present invention, the pH-adjusted alumina sol aqueous solution may be prepared using an alumina sol containing an acicular porous material represented by the following formula (1).

[Chemical Formula 1]

AlOOH-H ₂ O

Specifically, the pH-adjusted alumina sol aqueous solution may be prepared by adding distilled water to alumina sol having a pH of 2 to 9 to dilute and then adjusting the pH to 5 to 9, specifically 8 to 9 by adding a pH adjusting agent have.

At this time, the distilled water may contain about 1 to 2 parts by weight based on 100 parts by weight of the total alumina sol.

Ammonia may be used as the pH regulator, and the ammonia may include 0.2 to 4 parts by weight, specifically 0.4 to 2.8 parts by weight, based on 100 parts by weight of alumina sol. If the pH of the alumina sol aqueous solution is lower than 5, the alkali resistance of the coating film is lowered. If the pH of the alumina sol aqueous solution is more than 9 by adding a large amount of ammonia, And is converted into zirconium butoxide, which is one of the slurry components, to be gelated.

The method of the present invention may further include adding distilled water to the pH-adjusted alumina sol aqueous solution before the first hydrolysis reaction to form a more uniform mixture.

The distilled water may include 14 to 60 parts by weight, specifically 20 to 42 parts by weight, based on 100 parts by weight of alumina sol. If the distilled water content exceeds 60 parts by weight, the reactant is diluted and the subsequent reaction rate is lowered.

Also, in the method of the present invention, the zirconium compound may be used in combination with zirconium n-butoxide or zirconium propoxide and organic functional silane.

The zirconium compound may include 40 to 100 parts by weight, specifically 60 to 71 parts by weight, based on 100 parts by weight of alumina sol. If the content of the zirconium compound is less than 40 parts by weight, the heat resistance is lowered. If the content of the zirconium compound is more than 100 parts by weight, flaking of the coating film may occur.

Further, in the method of the present invention, the first hydrolysis reaction is preferably carried out at about 45 to 55 DEG C, specifically at 50 DEG C for 3 to 5 hours, for example, 4 hours. This first hydrolysis reaction produces an -OH group in each of the alumina sol and the zirconium butoxide compound to form an Al ₂ O ₃ -Zr bond (see Schemes 1 and 2 below). At this time, when the temperature of the hydrolysis reaction of t is out of the above range, the reaction efficiency is lowered and the yield is decreased, or the coating composition is gelated and it is difficult to perform uniform application.

[Reaction formula 1. Hydrolysis reaction of zirconium butoxide]

[Reaction formula 2. hydrolysis reaction of alumina sol]

Further, in the method of the present invention, the diatomaceous earth added in the second hydrolysis reaction is a component which imparts air purification and dew condensation preventing function, and is contained in an amount of 25 to 120 parts by weight, specifically 40 To 85 parts by weight. If the diatomaceous earth content is 25 parts by weight or less, the condensation effect is lowered. If the diatomite content is more than 120 parts by weight, cracking of the coating film occurs due to high viscosity.

The catalyst may be acetic acid. The catalyst may include 0.2 to 4 parts by weight, and 0.4 to 2.8 parts by weight based on 100 parts by weight of alumina sol.

The second hydrolysis reaction causes a condensation reaction of some Si-OH groups of the diatomite with some -OH groups of alumina sol. At this time, the second hydrolysis reaction is preferably carried out at about 75 to 85 ° C, specifically at 80 ° C for 3 to 5 hours, such as 4 hours. If the hydrolysis reaction temperature is out of the above range, the reaction efficiency is lowered and the yield is decreased, or gelation is caused and it is difficult to apply uniformly.

The method of the present invention may further include a fourth step of cooling the reaction product after the second hydrolysis reaction.

Also, an embodiment of the present invention provides an aqueous ceramic binder slurry prepared by the method of the present invention and an aqueous ceramic coating composition containing the same.

The aqueous ceramic coating composition may further comprise at least one additive selected from the group consisting of an aqueous ceramic binder slurry prepared by the method of the present invention and optionally a pigment, alumina, zirconium and filler.

In the aqueous ceramic coating composition of the present invention, the above-mentioned pigment is a component included for color development of a coating film without dissolving in water or most organic solvents, and is not particularly limited as long as it is a common pigment. For example, Further, pigments such as iron oxide sulfur or iron oxide red may be used in combination.

The pigment may comprise about 10 to 15 parts by weight based on 100 parts by weight of the aqueous ceramic binder slurry. If the content of the pigment is less than 5 parts by weight, the hiding power of the coating composition is lowered. If the content of the pigment exceeds 15 parts by weight, wetting of the aqueous slurry is lowered and chalking occurs.

In the aqueous ceramic coating composition of the present invention, the alumina or zirconium is contained as an ingredient for heat resistance enhancement, and may be used in combination with an organic material such as carbon or an inorganic material such as SiC, Si ₃ N ₄ and Zn. , But are not limited thereto.

The alumina or zirconium may each comprise about 2 to 10 parts by weight based on 100 parts by weight of the aqueous ceramic binder slurry. If the content of each component is less than 2 parts by weight, heat resistance is lowered. If the content of each component is more than 10 parts by weight, cracks of the coating film occur.

In addition, in the aqueous ceramic coating composition of the present invention, the filler is a component included in order to prevent cracking of a coating film, and is not particularly limited as long as it is a filler usually used in a coating composition. As typical examples thereof, Potassium titanate.

The filler material may include about 0.5 to 2.0 parts by weight based on 100 parts by weight of the aqueous ceramic binder slurry.

Further, in another embodiment of the present invention

Mixing the aqueous ceramic binder slurry prepared by the method of the present invention with at least one additive selected from the group consisting of pigments, alumina, zirconium and fillers; And

And dispersing the mixture using a ball mill. The present invention also provides a method for producing an aqueous ceramic coating composition.

At this time, it is preferable that the mixing step is performed using a ball mill.

In addition, it is preferable that the aqueous ceramic coating composition is dispersed in the form of powder having an average particle size of 20 mu m by the dispersing step.

As described above, in the present invention, by providing an aqueous ceramic coating composition using a pH-adjusted alumina sol aqueous solution, the -OH group of each compound is condensed to form a three-dimensional bond according to the -O- structure, It is suitable for coating various base materials, is easy to dry naturally, is environment-friendly because there is no poisonous gas generated when a film is formed or a fire is generated. Furthermore, since the aqueous ceramic coating composition of the present invention includes an aqueous ceramic binder, it is possible to maximize the condensation effect and the air purification effect without blocking the micropores in the coating film, and in particular, to enhance the color and heat resistance of the coating film, It is possible to obtain an effect of preventing the occurrence of cracks.

The environmentally friendly ceramic water-based coating composition according to the present invention is a coating material for interior or exterior coating of a building or a cement concrete structure, and more specifically, a cement concrete, a gypsum board, a medium density fiberboard (MDF) panel, It can be used for painting walls and ceilings made of other materials.

Hereinafter, a method for producing an aqueous ceramic coating composition according to the present invention and an aqueous ceramic coating composition prepared by the method will be described in detail with reference to the following examples. It should be understood that the specific embodiments of the present invention are not intended to limit the present invention but include all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention.

Example

(Examples 1 to 3)

Alumina sol (20 wt% Al ₂ O ₃ , pH 4, specific gravity 1.09-1.14, AS-520 unshiu) and distilled water were added to a four-necked flask equipped with a thermometer, a stirrer, a condenser and a stirrer to dilute ammonia And the pH of alumina sol aqueous solution was adjusted to 8 by stirring. Then, the pH-adjusted alumina sol was re-added with distilled water, uniformly stirred, and then zirconium butoxide was added thereto, and the first hydrolysis reaction was carried out for 4 hours while raising the temperature to 50 ° C. Then, diatomaceous earth and acetic acid were added dropwise to the reaction mixture, and the mixture was subjected to a secondary hydrolysis reaction while stirring the mixture for 3 hours while raising the temperature to 80 ° C to prepare an aqueous ceramic binder slurry.

At this time, the respective reactants were mixed in the content ratio (g) shown in Table 1 below.

After completion of the reaction, the obtained second hydrolysis reaction product was naturally cooled at room temperature.

Example 1 Example 3 Example 4 Alumina sol (g) 38.83 38.83 38.83 Ammonia (g) 0.252 0.25 0.25 Distilled water (g) 6.35 6.35 6.35 Zirconium butoxide (g) 22.84 22.84 22.84 Distilled water (g) 6.35 6.35 6.35 Diatomite (g) 25.13 35 10 Acetic acid (g) 0.25 0.25 0.25

(Examples 4 to 6)

Titanium dioxide, alumina powder, zirconium powder and potassium titanate were respectively mixed in the content ratios (g) shown in Table 2 below to the respective aqueous ceramic binder slurries prepared in Examples 1 to 3, Mu m to prepare an aqueous ceramic coating composition.

Example 4 Example 5 Example 6 Aqueous ceramic slurry (g) 79 79 79 Pigment: Titanium dioxide (g) 10 10 10 The alumina powder (g) 5 5 5 Zirconium powder (g) 5 5 5 Potassium titanate (g) One One One

(Comparative Examples 1 to 3)

Titanium dioxide, alumina powder, zirconium powder and potassium titanate were mixed into the aqueous ceramic binder slurry prepared in Example 1 at the content ratios shown in Table 3 below and then dispersed at an average particle size of 20 μm using a ball mill to obtain an aqueous ceramic paint A composition was prepared.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Aqueous ceramic slurry (g) 84 49 79.8 Pigment: Titanium dioxide (g) 5 30 10 The alumina powder (g) 5 5 5 Zirconium powder (g) 5 5 5 Potassium titanate (g) One One 0.2

(Experimental Example 1. Coating property test)

In order to test the coating properties of the coating compositions of Example 1 and Comparative Examples 1 to 3, a coating composition was coated on each of the aluminum specimens (coating thickness: 50 탆) and dried at a temperature of 50 캜 for 30 minutes. The physical properties such as natural drying, adhesion and water resistance were tested by the same test method, and the results are shown in Table 4 below.

[Test Methods]

1. Natural drying: Tacky phenomenon of the film after natural drying at 50 ° C for 1 day was evaluated.

2. Adhesiveness: After the cross-cut, the adhesive force was evaluated using a tape.

3. Water Resistance: After 7 days of immersion at 50 ° C, the appearance and adhesion of the film were measured.

Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Hiding power Good usually usually usually Water resistance Good Bad Bad Bad Natural drying Good usually usually usually Attachment Fermentation Bad Bad Bad Film surface condition Good usually Chalking occurs Cracking

(Experimental Example 2: Nonflammable Test)

The water-based ceramic coating composition of Examples 1 to 3 was applied on a siphon to form a coating film. Then, the coating film was formed on the surface of a siphon by the Korean Institute of Construction Materials Test (KS F ISO 1182: 2004) And non-combustibility tests were conducted. That is, in the above experiment, a metal (iron) specimen having a diameter of 45 mm and a height of 50 mm was tested by heating the entire surface of the aqueous ceramic coating composition (50 μm) for 20 minutes. The experimental results are shown in Table 5 (see Figs. 1 to 3).

[Test Methods]

Test apparatus: A heating furnace capable of raising 750 ° C

Test method: After raising furnace to 750 ℃, test specimen is put in furnace and heated for 20 minutes.

A) The average temperature of the thermocouple in the furnace is maintained at 750 ° C ± 5 ° C for 10 minutes.

B) Measure the mass of the specimen up to 0.01 g, insert it into the specimen holder, and put it into the furnace.

C) After heating for 20 minutes, remove the test holder from the furnace.

D) Measure the mass after cooling the specimen in a desiccator.

Performance criterion: The maximum temperature in the furnace for 20 minutes after the start of the heating test shall not rise above the final equilibrium temperature by more than 20 K (unless equilibrium is reached for 20 minutes, the final 1 minute average temperature shall be the final equilibrium temperature) The mass reduction rate of the specimen after completion should be 30% or less.

1) The specimen shall be of the same construction and material as the actual specimen.

2) The test shall be carried out three times for the specimen.

3) In the case of composite materials, there shall be no separate finish on each section of the specimen

(Experimental Example 3: Gas Harmfulness Test)

According to the test method of the Ministry of Construction and Transportation No. 2006-476 (KS F 2271: 2006) as follows, a gas harmfulness test was performed by measuring the behavior stopping time using a mouse of ICR pedigree, (See Figs. 4 to 6).

[Test Methods]

8 rats (ICR female, 5 weeks, 18-22 g) were placed in a spinning basket, and the specimen was placed in a heating furnace. After heating for 6 minutes (3 minutes of propane, 3 minutes of radiant heat), the combustion gas Go through the stirring box and go to the spin basket box to see the effect on the rat.

A) The temperature inside the test box is kept at 30 캜.

B) Put eight rotary baskets containing one experimental white rat in the test box.

C) The specimen is put into a heating furnace and heated for 6 minutes.

D) Measure the behavioral downtime of each experimental white rat for 15 minutes after initiation of heating.

Performance criteria: The average behavioral downtime of the experimental rats should be at least 9 minutes.

1) The specimen shall be of the same construction and material as the actual specimen.

2) The test shall be carried out twice on the side of the specimen which is in contact with the room.

3) In the case of composite materials, no separate finishing should be applied to each section of the specimen

Test Items unit Test result Criteria Test Methods Example 1 Example 2 Example 3 nonflammable
exam Mass reduction rate % 0.3 0.1 0.1 30 or less KS F 1SO
1182:
2004 Difference between peak temperature and final equilibrium temperature ℃ 0.7 0.8 2.1 Should not exceed 20 Gas hazard
exam Stop action
time min: s 12:50 12:46 - 9:00 or more KS F
2271: 2006

* Ministry of Land, Transport and Maritime Affairs Notice No. 2012-624 Complies with non-combustible material standards.

(Experimental Example 4)

The aqueous ceramic coating composition of Example 1 was applied on a siphon to form a coating film. Then, a condensation performance test and a fungicidal test were conducted on the coating film, and the results are shown in Table 6 below.

Test Items Example Test result Test Methods Condensation performance One clear LH Corporation Professional Specification: 2010 My mold One 9 KS M 6010: 2009 KSM 5000 is more than grade 6

As can be seen from the above Table 4, in the case of forming the coating film using the aqueous ceramic coating composition of Example 1 containing the pH-controlled alumina sol of the present invention, compared with the coating compositions of Comparative Examples 1 to 3, , The adhesion and the surface condition of the coating film can be improved.

In addition, referring to Table 5 and FIGS. 1 to 6, the water-based ceramic fireproof coating composition prepared according to the present invention has a very low mass reduction rate because it is hardly burned even at a high temperature and has a low difference in peak temperature and final equilibrium temperature, And it was confirmed that the behavior stoppage time of the mouse during burning exceeded the reference time, which is safe even in the case of gas harmfulness.

Furthermore, referring to Table 6, it can be seen that the aqueous ceramic coating compositions prepared in Examples 1 and 2 of the present invention show a great effect on dew condensation performance and fungus resistance.

Claims (22)

preparing an alumina sol aqueous solution having pH adjusted;
Introducing a zirconium compound into the alumina sol aqueous solution to perform a first hydrolysis reaction; And
And sequentially introducing diatomite and a catalyst into the resultant product of the first hydrolysis reaction and performing a second hydrolysis reaction. The method according to claim 1,
Wherein the aqueous alumina sol solution further comprises ammonia as a pH adjuster. The method according to claim 1,
Wherein the alumina sol aqueous solution has a pH of 5 to 9. < RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
Wherein the zirconium compound is a mixture of zirconium butoxide or zirconium propoxide with an organofunctional silane. The method according to claim 1,
Wherein the zirconium compound comprises 40 to 100 parts by weight based on 100 parts by weight of alumina sol. The method of claim 5,
Wherein the zirconium compound comprises 60 to 71 parts by weight based on 100 parts by weight of alumina sol. The method according to claim 1,
Wherein the first hydrolysis reaction is carried out at 45 to 55 DEG C for 3 to 5 hours. The method according to claim 1,
Wherein the diatomaceous earth comprises 25 to 120 parts by weight based on 100 parts by weight of alumina sol. The method of claim 8,
Wherein the diatomaceous earth comprises 40 to 85 parts by weight based on 100 parts by weight of alumina sol. The method according to claim 1,
Wherein the catalyst comprises acetic acid. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
Wherein the catalyst comprises 0.2 to 4 parts by weight based on 100 parts by weight of alumina sol. The method of claim 11,
Wherein the catalyst comprises 0.4 to 2.8 parts by weight based on 100 parts by weight of alumina sol. The method according to claim 1,
Wherein the second hydrolysis reaction is carried out at 75 to 85 ° C for 3 to 5 hours. The method according to claim 1,
Wherein the method further comprises cooling after the second hydrolysis reaction. ≪ RTI ID = 0.0 > 11. < / RTI > An aqueous ceramic binder slurry prepared by the method of claim 1. An aqueous ceramic binder slurry according to claim 15,
Optionally at least one additive selected from the group consisting of pigments, alumina, zirconium and fillers. 18. The method of claim 16,
Wherein the pigment comprises 5 to 15 parts by weight based on 100 parts by weight of the whole aqueous ceramic binder slurry. 18. The method of claim 16,
Wherein the pigment is titanium dioxide. 18. The method of claim 16,
Wherein the pigment is a mixture of iron oxide yellow and iron oxide yellow. 18. The method of claim 16,
Wherein the alumina comprises 2 to 10 parts by weight based on 100 parts by weight of the whole aqueous ceramic binder slurry,
Wherein the zirconium comprises 2 to 10 parts by weight based on 100 parts by weight of the whole aqueous ceramic binder slurry. 18. The method of claim 16,
Wherein the filler comprises 0.5 to 2.0 parts by weight based on 100 parts by weight of the whole aqueous ceramic binder slurry. 18. The method of claim 16,
Wherein the filler is potassium titanate having a particle diameter of 1 占 퐉 or less.

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