KR20060042649A - Wall paint composition using natural protein binder - Google Patents

Abstract

The present invention relates to a wall coating material for building interior wall finishing, and more particularly to a human-friendly natural wall coating material using a natural binder. The present invention includes water 2-10%, protein fiber resin 10-30 wt%, filler 30-60wt%, porous mineral material 5-30wt%, inorganic pigment 1-10wt%, visible light responsive photocatalyst powder 0.1-5wt% It provides a natural wall covering composition. According to the present invention, it is possible to provide a harmless environmentally friendly wall covering material for humans, and the recycling of waste resources can also provide a great resource saving effect and lower the manufacturing cost of the wall covering material. In addition, despite the increase in the thickness of the coating film, not only the mechanical properties of the coating film are improved, such as reducing the occurrence of cracks, but also the condensation characteristics are superior to the conventional wall covering materials.

Natural binder, protein fiber resin, calcium carbonate, egg shell, crack

Description

Wall coating material composition using natural protein-based resin {WALL PAINT COMPOSITION USING NATURAL PROTEIN BINDER}

The present invention relates to a wall coating material for building interior wall finishing, and more particularly to a human-friendly natural wall coating material using a natural binder.

Currently, most wallpaper used indoors are vinyl chloride wallpaper. However, the wallpaper is highly toxic as a plasticizer and contains a large amount of formaldehyde as an adhesive and a phthalic acid compound (DBP), which is known as an endocrine disruptor. Moreover, since most of the wallpaper contains a large amount of organic chlorine compounds as monovinyl chloride wallpaper, there is a high possibility that dioxins are generated upon incineration. In addition, the wallpaper is poorly breathable and may cause secondary pollution due to mold generation caused by moisture.

Accordingly, researches to replace wallpaper with bio-wall paints are being actively conducted. For example, Japanese Patent Application Laid-Open No. 10-183023, wherein the wall covering composition of the publication includes a pigment and an inorganic oxide in a carbonyl group-containing copolymer emulsion containing a hydrazine derivative, and the inorganic oxide is Photocatalytic activity. However, the composition having a synthetic resin emulsion as described above may cause chemical hypersensitivity by generating some volatile organic compounds due to the presence of some unreacted monomer in the emulsion.

In addition, Japanese Patent Laid-Open No. 2003-336374 discloses a wall covering composition comprising bamboo charcoal, a binder and a pigment. However, the above patent also uses methyl cellulose, vinyl acetate emulsion, or water-soluble urethane resin as a binder, and the above-mentioned problems cannot be avoided. In addition, although the patent claims that the absorption effect of the chemical, including diatomaceous earth, silica sand, vermiculite, pearlite, etc. to obtain the far-infrared effect and the electromagnetic wave adjustment effect, it does not present specific data that can be recognized.

In addition, the patents are not suitable for application to houses or buildings in Korea because they do not exhibit sufficient adhesion strength to the walls when applied to cement or concrete walls.

In addition, most of the wall coating materials currently commercialized are manufactured by adding a synthetic resin emulsion as a binder and adding mineral raw materials such as ganbanite, jade, ocher, illite, and s Korea to exhibit bio characteristics. However, this conventional coating material is difficult to fundamentally block volatile organic compounds because it uses a general synthetic resin emulsion. In addition, these raw materials are expensive products, and do not exhibit sufficient bio performance, and there is a lack of verified data on the bio-characteristic effects of natural mineral raw materials such as elvan and jade.

In particular, as the public's interest in chemical hypersensitivity has increased due to the recent court ruling on the new house syndrome and the indoor air quality control law has been implemented, the demand for natural new wall covering materials is urgently needed.

On the other hand, the peculiar smell of the birdhouse is due to the smell of cement concrete framing and the harmful gases emitted from various building materials, which causes symptoms such as atopic dermatitis, rhinitis, asthma, itching, cough, and vomiting in inmates. do. In order to reduce these harmful gases, a material called a bio-ceramic coat may be coated inside the wallpaper, and most of these materials are manufactured by adding non-toxic or low-toxic organic-inorganic binders and natural far-infrared emitter materials such as jade, ocher and elvan. . However, this material can be expected to inhibit the toxicity of cement as a wall coating material coated inside the wallpaper, but there is a limit to suppress the formaldehyde emitted from the wallpaper adhesive.

As such, the conventional wall covering material is not suitable for the Korean residential environment, and does not show satisfactory performance in recent environmentally-friendly characteristics, bio characteristics, deodorization characteristics, etc., and thus, there is an urgent need for new wall coating materials. to be.

The present invention is to solve the above problems of the prior art, using a natural binder, harmless to the human body, inexpensive and at least a certain thickness does not occur cracks, excellent workability and adhesion, antibacterial, anti-mildew An object of the present invention is to provide a functional natural wall covering having excellent deodorization and condensation inhibiting performance.

In order to achieve the above technical problem, the present invention provides water 2-10%, protein fiber resin 10-30wt%, calcium carbonate 30-60wt%, porous mineral material 5-30wt%, inorganic pigment 1-10wt%, visible light response type It provides a natural wall covering composition comprising 0.1 ~ 5wt% photocatalyst powder.

In the present invention, the protein fiber resin is preferably a reaction mixture of egg shell membrane, metal complex and plant tannin. In addition, the calcium carbonate is preferably heavy calcium carbonate having a particle size of 5 ~ 50㎛. In the present invention, the porous inorganic pigment preferably comprises at least one material selected from the group consisting of diatomaceous earth, synthetic calcium silicate, synthetic magnesium silicate, syras, syras balun, zeolite and s Korea.

Hereinafter, the present invention will be described in detail by explaining preferred embodiments of the present invention.

The natural wall covering composition of the present invention comprises a protein fiber resin, a filler, a porous mineral material, an inorganic pigment, and a visible light responsive photocatalyst powder, wherein the specific composition, content and each component of each component in the composition of the present invention The function performed in the composition is as follows. However, the function of the composition of the present invention described below is based on the general facts known to the present inventors, and does not mean that these components are necessarily limited to this function.

a. Protein cellulose resin

Protein fiber resin in the composition of the present invention serves as a binder as a composite polymer particles containing protein fiber. The protein fiber resin may be prepared from various raw materials. For example, the protein fiber resin of the present invention can be prepared from a living egg shell of an egg. An example of the manufacturing method of the said protein fiber resin is as follows.

In the reaction bonding process, 1.3 to 30 parts by weight of an aqueous solution of a complex compound and an aluminum sulfate solid content of 3 to 30% were added to 100 parts by weight of the biological egg shell membrane mixed with water having a solid content of 5 to 30%, and the pH was 3 to 6, 20 to 100 ° C. Coordination-binding protein polymer is prepared at the temperature of. Subsequently, 0.5 to 30 parts by weight of plant tannin is added, and the coordination-bound protein polymer is reacted with tannin at a temperature of 20 to 100 ° C. Next, 0.5 to 30 parts by weight of the rosin soap prepared by saponification of the rosin resin and 0.3 to 30 parts by weight of the dry oil and the sulfa compound were added, and 0.05 to 0.2 parts by weight of the cobalt naphthenic acid metal salt was mixed with 100 parts by weight of the linseed oil. The resin filling process is performed by polymerization at 40 to 100 ° C. for 24 hours. Next, 0.5 to 30 parts by weight of an alkali metal salt, sodium hydroxide or potassium hydroxide aqueous solution is added for emulsification, and cleavage reaction is carried out at a temperature of 30 to 120 ° C. for 1 to 72 hours to form hydrogen bonds between peptide chains of the nonpolar tertiary structure of the protein. Only 10 to 50% cleavage partially denatures the protein, shears it into fine particles, and then acts as a hydrophilic surfactant of the hydroxy (OH) group in the emulsion to induce the water dispersion of the uncleaved peptide hydrophobic protein fibrin particles. Subsequently, it is simply sheared by the usual sharp blade rotation, ball mill, etc., and the protein fiber resin of the emulsion state of 50-5,000 nm particle size can be obtained.

The protein fiber resin thus prepared masks odors and does not easily decay even in a wet state, and has a property of being easily dispersed in an aqueous solution.

In addition, the composition of the present invention does not use a synthetic resin emulsion unlike the conventional wall coating material as a binder, there is no release of human harmful substances, which is a problem in the conventional binder, the natural produced from the egg shell membrane used in the present invention The binder has better air permeability than general synthetic resins due to the nature of the spongy structure of the polypeptide fibers of the spongy structure formed naturally during the biosynthesis of eggs.

Furthermore, by recycling the discarded egg shell membrane, not only the effect of saving resources, but also the wall covering material which is cheaper than the existing wall covering material can be manufactured. It is preferable that the natural protein fiber resin of this invention contains 10 to 30% weight with respect to the composition total weight.

b. Filler

The filler in the composition of the present invention serves to suppress the occurrence of cracks even when applied over a certain thickness.

The filler of the present invention may be designed to reflect the following design matters in order to suppress the occurrence of cracks. First, the filler in the present invention preferably has a wide particle size distribution. The wider the particle size distribution, the higher the packing density of the wall covering material and the lower the porosity, so that the occurrence of cracks can be suppressed even when the coating film thickness increases.

In addition, the filler of the present invention preferably has a low oil absorption amount. Oil absorption refers to the amount of linseed oil (cc / 100g pigment) required to make a paste with a certain flow rate after adding refined linseed oil to the pigment to form a paste. Oil absorption is understood as the amount of oil needed to surround the surface of the organic pigment and again fill the space between the pigment particles and the particles. In other words, the finer the particles of the pigment, the larger the oil absorption amount. This is because the specific surface area (surface area per unit weight) of the pigment becomes large, and the oil absorption amount and the specific surface area have a strong positive correlation with each other.

In view of the foregoing, it is preferable that the filler of the present invention has a low oil absorption and a low specific surface area. If the oil absorption amount is small, dry shrinkage occurs after drying of the wall covering material, so that cracking can be prevented.

Calcium carbonate may be used as the filler in the present invention. Calcium carbonate has the advantages of excellent whiteness and opacity, easy color adjustment, high hydrophilicity, low oil absorption, and excellent homogeneity of the product.

Calcium carbonate can be generally classified into calcium carbonate, heavy calcium carbonate, hard calcium carbonate and the like depending on the particle size and the manufacturing process. Usually calcium carbonate refers to the granulated calcium carbonate, the particle diameter of up to several mm ~ 400 mesh. Heavy calcium carbonate (Ground Calcium Carbonate) is manufactured by physically grinding and classifying high purity crystalline limestone (Calcite) having high whiteness. Although the particle size range of heavy calcium carbonate is not clear, it refers to the product of about 325mesh (45㎛) or less. Recently, with the development of powder technology and classification equipment, the average particle diameter is produced to the product of 1㎛ or less. Precipitated Calcium Carbonate (Crecipitated Calcium Carbonate) is a calcium carbonate produced by a chemical manufacturing method using limestone as a raw material. It is also called precipitated calcium carbonate. Precipitated calcium carbonate can control the particle shape, particle diameter, particle size distribution and the like according to the production conditions.

The physical properties of the aforementioned calcium carbonate are listed in Table 1 below. From the specific surface area and oil absorption characteristics of the calcium carbonates listed in Table 1, it can be seen that it is preferable to use heavy calcium carbonate in these calcium carbonates. The heavy calcium carbonate preferably has a wide particle size distribution, preferably a large particle size of 5 ~ 50㎛. Heavy calcium carbonate in the above-mentioned particle size range can suppress the occurrence of cracking even at a thickness of 3 mm or more. The filler of the present invention is preferably included 30 to 60% by weight based on the total weight of the composition.

Kinds Ordinary calcium carbonate Heavy calcium carbonate Hard calcium carbonate Slight Calcium Carbonate Ultra-Calcium Carbonate Microporous Activated Calcium Carbonate Specific surface area (㎡ / g) 6.6 2.5 4.8 31 31 Oil absorption (cc / 100g) 28 28 42 45 30

c. Porous mineral materials

 In the present invention, a porous mineral material is used to improve the condensation properties of the wall covering material. The porous mineral material improves condensation properties by hygroscopic or hygroscopic action, and adsorbs gases harmful to the human body to improve the deodorizing performance of the wall covering material.

In the present invention, the porous mineral material is preferably added 5 to 30% by weight. As the porous mineral usable in the present invention, diatomaceous earth, synthetic silicates, syras, syras balun, zeolite, s Korea and the like may be used, and these materials may be used alone or in combination of one or more.

In the present invention, as the porous mineral material, it is preferable to use diatomaceous earth having physicochemical stability and porosity, mainly composed of amorphous silica. Diatomaceous earth has the advantage of being light, absorbent and excellent in heat insulation.

 In addition, as the silicates used as the porous mineral material, calcium silicate or magnesium silicate prepared by hydrothermal reaction of diatomaceous earth and hydrated lime may be used. These silicates are suitable for use as the filler of the present invention because of their low apparent specific gravity, high absorbency and oil absorption, high specific surface area, and various particle shapes and structures.

The porous mineral material added in the present invention can also function as an inorganic pigment.

d. Inorganic pigments

The composition of the present invention also includes an inorganic pigment. The use of inorganic pigments in paints not only paints the paint but also makes the coating opaque and hides the lower limbs. In addition, the inorganic pigment is chemically stable and has the advantage of preserving the color completely against the action of sunlight or the atmosphere. Table 2 below shows the hiding power of the white pigments usable in the present invention. Referring to the table below, it can be seen that among the white pigments listed, rutile type titanium oxide has the highest hiding power, and thus is most suitable for use in the wall covering composition of the present invention. In addition, the inorganic pigment of the present invention may further include a sieving pigment, such as calcium carbonate, talc, kaolin, in addition to the pigments listed in Table 2 below.

In the present invention, the inorganic pigment is preferably added 1 to 10% by weight based on the total weight of the composition, the average particle size of the pigment is preferably 40 μm or less.

Kinds Titanium oxide (rutile) Titanium Oxide (Anatase) Zinc oxide white lead Lithopone Zincification Hiding power (㎠ / g) 294 230 116 30 54 40

e. Visible Light Responsive Photocatalyst Powder

The visible light responsive photocatalyst powder included in the composition of the present invention sterilizes bacteria or the like attached to the wall surface or decomposes harmful substances to human body to reduce indoor pollution. Titanium dioxide having a crystal structure of anatase phase is generally used as the photocatalyst. However, while titanium dioxide on anatase phase has excellent photoactivity in the ultraviolet region, photoactivity in the visible region is insignificant. Therefore, in the present invention, in order to improve the deodorization and bio-characteristics in the indoor light, oxygen-depleted titanium dioxide made by doping metal cations or anions doped with titanium oxide, or using titanium dioxide having a crystalline structure of the burukaite phase Powder products can be used. In addition, it is also possible to use a silica photocoating treatment on titanium dioxide or to use a hybrid photocatalyst complexed with apatite so as to prevent deterioration of properties due to organic substances.

 The visible light responsive photocatalyst powder is preferably added in an amount of about 0.1 to 5% by weight based on the total natural wall covering composition.

f. Other additives

Although not essential to the present invention, a dispersing agent, an antifoaming agent, a preservative, and the like, which are usually used in paints, may be added to improve coating properties, and these additives preferably include 0.5 to 3% by weight based on the total weight.

As the dispersant, one or more substances selected from the group consisting of naphthalene sulfonate formalin condensates, melamine sulfonate formalin condensates, polycarboxylic compounds, polycarboxylic ethers, aromatic amino sulfonic acid polymers, and metal salts of lignin sulfonic acid may be used. As the foaming agent, a defoaming agent of a mineral oil-based, silicone-based and other series may be used.

g. Dispersion

In order to uniformly mix the composition of the present invention, about 2 to 10% by weight of water may be included based on the total weight of the composition.

 The natural wall covering material of the present invention including the above-mentioned components may be applied to the wall surface by various methods such as a roller, a brush, a trowel, and an air spray according to a coating method in a liquid putty type. In this case, in order to obtain a smooth workability, in the case of brush painting, within 5% by weight, in the case of roller coating, within 10% by weight, and in the case of spray coating, water may be further mixed and used.

On the other hand, the conventional wall coating material has to remove the existing wallpaper and paint, but the natural wall coating material of the present invention can be easily painted on the wallpaper, so it has the advantage that it is possible to construct not only new construction, but also when remodeling existing buildings. .

Example

In order to grasp the crack according to the filler and particle size distribution of the present invention by applying the composition of the three formulations as shown in Table 3 below was set to three formulation ratios, the condensation and workability according to the porous inorganic pigment Evaluated. The workability and appearance of cracks and trowels were also evaluated. In Table 3 below, calcium carbonate-A, calcium carbonate-B, and calcium carbonate-C are heavy calcium carbonates having different particle sizes. As the inorganic pigment, a mixture of rutile titanium dioxide and calcium carbonate, talc and kaolin was used.

In this embodiment, as the photocatalyst, a visible light responsive photocatalyst powder was used as an oxygen deficient titanium dioxide photocatalyst powder of Ecodevice, Japan, and an inorganic pigment was used as rutile titanium dioxide, and as other additives. Naphthalene sulfonate formalin condensate and mineral oil antifoam were used.

ingredient Example 1 (% by weight) Example 2 (% by weight) Example 3 (% by weight) Protein cellulose resin 20 20 20 Filler Calcium Carbonate-A (Average Particle Size 44㎛) 40 30 20 Calcium Carbonate-B (Average Particle Size 21㎛) - 5 10 Calcium Carbonate-C (average particle size 10㎛) - 5 10 Porous mineral materials Diatomaceous earth 20 15 10 Calcium silicate - 5 10 Syrasballoon 5 5 5 Photocatalyst 3 3 3 Inorganic pigments 10 10 10 Other additives 2 2 2 Sum 100 100 100

Coating properties were tested by mechanical and chemical properties, workability, affinity properties, bio, condensation and deodorization. For mechanical and chemical properties, adhesion strength, washing resistance, alkali resistance and cracking resistance according to initial drying were measured according to the KS F 4715 standard, and the evaluation of crack occurrence over 3 mm of film thickness was evaluated as follows.

 The wall covering composition of Table 3 was applied to the chestnut plate at a thickness of 3 mm. After drying at room temperature for 24 hours, the dry film thickness was measured using a film thickness meter, and the occurrence and appearance of cracks were visually evaluated. Workability was evaluated by directly painting using a trowel.

In order to measure the environmentally friendly characteristics, the emissions of TVOC and HCHO, which are hazardous gases, were measured by a small chamber method using a passive sampler. For the measurement of the bio-characteristics, the microbial reduction rate by pressure adhesion method and the antifungal properties by ASTM G 21 were measured.

Deodorization characteristics were measured by the deodorization rate of ammonia after 120 minutes by KICM-FIR.

In addition, the dew condensation characteristic of the coating film used the following measuring method. First, a bronze cone having a height of 27.5 cm, a diameter of 15 cm, and a thickness of 400 μm is manufactured, and the brush is painted 3 to 4 times so that the dry film thickness is 200 to 300 μm and left at room temperature. Dried for 2 days. After drying, the thickness of the coating film was measured, and a mark for checking ink bleeding was marked with an aqueous sign pen. Subsequently, a bronze cone was installed in a constant temperature and humidity chamber maintained at a humidity of 60 to 70% and an internal temperature of 18 to 20 ° C., and a beaker was placed under the bronze cone to measure the weight of the dew condensation water. The inside of the bronze cone was continuously added to ice water and maintained within 5 ° C., and the time was observed by visually observing the initial condensation start time and ink bleeding on the surface of the cone. The test was terminated three hours after the start of the test. The weight of the condensation water was calculated including the amount of water collected in the beaker and the weight of water contained in the coating film. The weight of the moisture contained in the coating film was calculated from the weight change of the bronze cone coated with the coating film before and after the test. This method is the same as the method described in Korean Patent Application No. 10-2001-0049635 of the applicant.

As Comparative Example 1, a coating film was manufactured in the same manner as in the above-described example using Venus-coat, a product name of NIHON M TECS Co., Ltd., whose main material was volcanic ash as a binder and a synthetic resin emulsion. Was measured.

 Example 2 described above after mixing in a slurry mixer with 80% by weight of water relative to solid content using a diatomaceous earth wall material, Fujiwara Chemical Co., Ltd. product name clean-up In the same manner as in the coating film was prepared and its physical properties were measured.

Table 4 and Table 5 show the measurement results of the physical properties of the above-described Examples and Comparative Examples.

division Item Experiment result How to measure Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Coating properties Low temperature stability clear clear clear clear clear KS F 4715 Cracking resistance due to initial drying clear clear clear clear clear Bonding strength (n / mm2) 0.65 0.70 0.75 0.60 0.10 Wash resistance clear clear clear clear Has abnormal Alkali resistance clear clear clear clear clear Crack (3 mm or more) Does not occur Does not occur Does not occur Occurs Occurs Self experiment Workability (trowel) Good Good Good Good Good Exterior Good Good Good Good usually Environmental characteristics TVOC (mg / ㎡h) Less than 0.2 Less than 0.2 Less than 0.2 Less than 0.4 Less than 0.2 Small chamber method HCHO (mg / ㎡h) Less than 0.01 Less than 0.01 Less than 0.01 Less than 0.05 Less than 0.01 Bio properties % Reduction More than 99% More than 99% More than 99% More than 99% More than 99% Pressure bonding Antifungal Can't grow Can't grow Can't grow Can't grow Mold development ASTM G 21 Deodorization Rate (Ammonia) 99.9% 99.9% 99.9% 90% 88.2% KICM -FIR

Item Experiment result Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Initial condensation time Visual observation 2:00 Not observed Not observed 1:10 1:45 Ink smear 2:20 Not observed Not observed 1:30 1:32 The amount of condensation collected on the paint (g) 12.5 15.7 18.3 13.5 15.3 The amount of condensation collected in the beaker (g) 3 none none 20.4 10.5

As can be seen from Table 4, the natural wall coating material of the present invention is superior in the adhesive strength compared to the existing wall coating material composition, and cracks do not occur even beyond a certain coating thickness. In addition, also in the environmental characteristics, it turns out that the generation amount of harmful gas is drastically reduced compared with the comparative examples 1 and 2. In addition, the wall covering composition of the present invention shows an excellent deodorizing effect compared to Comparative Examples 1 and 2.

 Referring to Table 5, it can be seen that the comparative example is less condensation characteristics than the embodiments of the present invention. In Examples 2 and 3, neither ink bleeding nor visual observation of dew condensation and no condensation water collected in the beaker showed that the condensation inhibiting effect was enhanced by the addition of calcium silicate and syras balun rather than the use of diatomaceous earth alone. Able to know. In addition, as the content of diatomaceous earth increases, it is confirmed that the adhesion ratio of diatomaceous earth should be well controlled because the adhesion of the trowel is difficult to work.

According to the present invention, the natural wall covering material of the present invention can obtain an environmentally friendly product which is harmless to human body compared with the conventional one by using a protein fiber resin natural binder as a binder. In addition, in the case of using the biological egg shell membrane as a raw material of the natural binder, by using the resources that have been previously discarded, the resource saving effect is also large, and the manufacturing cost of the wall covering material can be lowered.

In addition, the natural wall coating material of the present invention can form a thick coating film conventionally by adjusting the particle size distribution and oil absorption amount of the filler, and the occurrence of cracking is reduced despite the increase in the coating film thickness.

In addition, the composition of the present invention has almost no emission of harmful components to the human body, and exhibits superior properties in comparison with conventional wall coverings not only in the mechanical properties of the coating film, but also in environmentally friendly and condensation properties.

Claims (4)

Natural wall containing 2 ~ 10% water, 10 ~ 30wt% protein fiber resin, 30 ~ 60wt% calcium carbonate, 5 ~ 30wt% porous mineral material, 1 ~ 10wt% inorganic pigment, 0.1 ~ 5wt% visible light responsive photocatalyst powder Application composition. The method of claim 1, The protein fiber resin is a natural wall covering composition, characterized in that the reaction mixture of eggshell membrane, metal complex and plant tannin. The method of claim 1, The calcium carbonate is natural wall covering composition, characterized in that it comprises a heavy calcium carbonate having a particle size of 5 ~ 50㎛. The method of claim 1, The porous mineral material comprises at least one material selected from the group consisting of diatomaceous earth, synthetic calcium silicate, synthetic magnesium silicate syras, syras balun, zeolite and s Korea.