KR102535233B1 - Water-soluble coating composition with excellent adhesion strength - Google Patents

Abstract

In the present invention, disclosed is a water-soluble coating composition that increases the adhesion strength of a coating film by reducing the total amount of inorganic substances added and does not leave inorganic powders even after the coating film is dried by adding a porous metal organic framework (MOF), which has excellent antibacterial, deodorizing, and moisture-absorption and desorption effects, as a main component of an inorganic powder. The water-soluble coating composition with excellent adhesion strength according to an embodiment of the present invention includes: a binder resin containing an acrylic polymer compound, an inorganic solvent, a thermal polymerization initiator, and an acid; and inorganic powders including silica, zeolite, diatomaceous earth, and porous MOF. The acrylic polymer compound is an acrylic polymer compound having an amine group or a complex in which dissociated casein is bound to at least a portion of the surface of the acrylic polymer particle.

Description

Water-soluble coating composition with excellent adhesion strength {Water-soluble coating composition with excellent adhesion strength}

The present invention relates to a water-soluble paint composition for architectural finishing having excellent moisture absorptive and desorptive ability and excellent adhesion strength, and a painting method using the same.

A building finishing material is a typical building material that is attached to the surface of the inner wall, floor, or outer wall of a building made of cement concrete, wood, MDF, gypsum board, etc. refers to exterior materials. Toxic gases such as ammonia are released from cement concrete, and most of the solvents used in adhesives for bonding building finishing materials contain formaldehyde, toluene, and volatile organic compounds (VOC) that are harmful to health, such as toluene and xylene. there is.

As a result, interest in eco-friendly materials has increased more than ever as a finishing material for residential buildings, and eco-friendly inorganic materials mixed with bioceramics and natural minerals are used as building finishing materials. When stored for a long time, precipitation is easy to occur, and workability is poor during painting.

In addition, due to excessive input of a moisture absorption and desorption material, which is a key inorganic material, the strength of the coating film is weak, adhesion and adhesion strength are reduced, and inorganic materials remain on the hand even after the coating film is dried. Therefore, there is a need to improve a paint composition for architectural finishing painting having excellent adhesion strength while maintaining physical properties such as moisture absorption and desorption, antibacterial, and deodorization while lowering the content of inorganic substances in the paint composition.

In the present invention, by adding a porous metal organic framework (MOF), which has excellent antibacterial, deodorizing, and moisture absorption and desorption effects, as the main component of the inorganic powder, the total amount of inorganic substances added is reduced to increase the strength and adhesion strength of the coating film and dry the coating film. It is an object of the present invention to provide a water-soluble coating composition in which inorganic powder does not remain even after use.

Technical tasks to be achieved in the embodiments are not limited to those mentioned above, and other technical tasks not mentioned will be considered by those skilled in the art from various embodiments to be described below. can

A water-soluble paint composition having excellent adhesion strength according to an embodiment of the present invention includes a binder resin containing an acrylic polymer compound, an inorganic solvent, a thermal polymerization initiator, and an acid; and inorganic powder including silica, zeolite, diatomaceous earth, and a porous metal organic structure (MOF), wherein the acrylic polymer compound is an acrylic polymer compound having an amine group or casein dissociated to at least a part of the surface of the acrylic polymer particle. is a complex

Further, according to an embodiment of the present invention, the binder resin may include 100 parts by weight of an acrylic polymer compound, 40 to 80 parts by weight of an inorganic solvent, 1 to 10 parts by weight of a thermal polymerization initiator, and 5 to 10 parts by weight of an acid. .

In addition, according to one embodiment of the present invention, the inorganic powder contains 10 to 20 parts by weight of zeolite, 10 to 30 parts by weight of diatomaceous earth, and 20 to 50 parts by weight of a porous metal organic structure (MOF) based on the total weight of the binder resin, The blending weight ratio of the binder resin and the inorganic powder may be 100:70 to 90.

In addition, according to an embodiment of the present invention, the porous metal organic structure is Cu/ZIF-67 in which copper is deposited and bonded and CDs/ZIF-67 in which carbon dots are deposited and bonded, and the Cu/ZIF-67 and CDs/ZIF are combined by deposition. -67 may be added in a mixing ratio of 1:2 to 4.

In addition, according to an embodiment of the present invention, the copper (Cu) particles deposited on the Cu/ZIF-67 are 5 to 15% by weight, and the carbon points deposited on the CDs/ZIF-67 are 5 to 10% by weight. can be

In addition, another embodiment of the present invention is a painting method for interior architectural finishing using the water-soluble paint composition, comprising the steps of removing foreign substances attached to the surface of the surface to be coated; forming a finishing layer with a thickness of 0.3 to 0.5 mm by applying the water-soluble paint composition having excellent adhesion strength; and drying the finishing layer.

According to the embodiments, by adding a CDs / ZIF-67 organometallic structure with excellent moisture absorption and desorption performance and a Cu / ZIF-67 organometallic structure with excellent antibacterial / deodorizing ability as the main inorganic component, a pigment for functioning, Compared to other coating compositions in which a significant amount of inorganic materials such as ceramics are added, not only can a superior effect be obtained with a minimum amount of inorganic powder, but also the strength and adhesion strength of a coating film can be improved.

In addition, the coated paint composition can solve the problem of floating due to a large amount of inorganic substances and poor adhesion or staining of inorganic substances on the surface of the coating film even after drying.

The water-soluble coating composition according to the present invention not only exhibits antibacterial, deodorizing and moisture absorption and desorption effects with a minimum amount of inorganic powder compared to other coating compositions in which a significant amount of inorganic materials are added, but also can improve the strength and adhesion of the coating film. It is applied to the surface of wood, gypsum board, cement concrete, as well as steel buildings with excellent adhesion even with a thin thickness, so that defects such as lifting can be prevented during subsequent processes such as wallpapering, and it has antibacterial activity even when used as a final coating film. It is harmless to the human body, eco-friendly, and can solve the problem of inorganic substances on the surface of the coating film.

Effects obtainable from the embodiments are not limited to the effects mentioned above, and other effects not mentioned are clearly derived and understood by those skilled in the art based on the detailed description below. It can be.

Throughout the specification, when a part is said to "comprising" or "including" a certain element, it means that it may further include other elements, not excluding other elements, unless otherwise stated. do. In addition, terms such as “… unit”, “… unit”, and “module” described in the specification mean a unit that processes at least one function or operation, which is hardware or software or a combination of hardware and software. can be implemented as Also, “a or an”, “one”, “the” and like terms are used herein in the context of describing various embodiments (particularly in the context of the claims below). Unless otherwise indicated or clearly contradicted by context, both the singular and the plural can be used.

The water-soluble paint composition having excellent adhesion strength according to the present invention includes 100 parts by weight of an acrylic binder resin and 20 to 50 parts by weight of an inorganic powder having excellent antibacterial, antifungal, moisture absorption and deodorization properties.

In the present invention, the 'acrylic polymer compound' may include an acrylic compound and a methacrylic compound, and the 'acrylic group' may include an acrylic group and a methacrylic group. The binder resin constituting the water-soluble paint composition of the present invention may include an acrylic resin.

The binder resin may include 100 parts by weight of an acrylic polymer compound, 40 to 80 parts by weight of an inorganic solvent, 1 to 10 parts by weight of a thermal polymerization initiator, and 5 to 10 parts by weight of an acid.

The acrylic compound, which is a basic unit of the acrylic polymer compound, may be selected from the group consisting of acrylic acid, acrylate compound, methacrylic acid, methacrylate compound, and mixtures thereof, or a mixture thereof. Specifically, the acrylic compound is methyl methacrylate (MMA), dimethylaminoethyl methacrylate (DMAEMA), diethylaminoethyl methacrylate (DEAEMA), normal isopropyl acrylamide (NIPAM), acrylomolepine ( ACMO), N,N-dimethylacrylamide (DMAA), N,N-diethylacrylamide (DEAA), acrylamide (AAM), N-butoxymethylacrylamide (N-BMAA), I-butoxymethyl Acrylamide (I-BMAA), N-hydroxyethylacrylamide (N-HEAA), N-methylolmethacrylamide (N-MMAA), butyl acrylate (BAM), acrylic acid, methacrylic acid, methyl acrylate , ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, ethylhexyl acrylate, 2-hydroxy Roxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, lauryl acrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate acrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, lauryl methacrylate, and mixtures thereof can be selected from the group.

In addition, the acrylic compound of the present invention may include an amine group in a repeating unit, and the ratio of having an amine group in the polymerized acrylic compound is preferably 10% or more, and the upper limit may be 60% or less. As the acrylic compound into which an amine group is introduced is essentially included as a repeating unit, the paint composition of the present invention can improve appearance after painting, scratch resistance, hardness, and chemical resistance.

The amine group may be ionized to increase water dispersibility, and a water-soluble acrylic resin may be formed through water dispersion after formation of cations such as ammonium through an acid, which is a component of a binder resin to be described later. In addition, the amine group induces a reaction between the organic material and the inorganic material and forms a chemical bond to increase the bonding strength of the coating film, thereby improving the adhesion strength and the coating film strength.

The acrylic compounds may be interconnected by the dissociated casein, thereby improving cross-linking and/or binding properties between the complexes. As a result, it can show strong adhesion not only to wood and cement concrete, but also to materials that have relatively poor adhesion to water-based paints, such as steel.

The acrylic polymer compound may be formed by polymerizing acrylic monomers in the presence of casein dissociated by adjusting the pH. As the thermal polymerization initiator, any initiator known in the art to which the present invention pertains may be used without limitation. For example, polymerization may be initiated using a known organic peroxide initiator such as ammonium peroxide sulfate or potassium peroxide sulfate. Specifically, benzoyl peroxide, dibutyl peroxide, t-butylperoxybenzoate, t-butyl Peroxy(2-ethylhexanoate), AIBN (azobisisobutyronitrile) or mixtures thereof may be used. In addition, when the polymerization is initiated after saponification of the acrylic monomer, the mixing property with casein is improved, and thus the formation of the complex may be facilitated.

The casein-bound acrylic polymer compound complex may have a casein concentration of 1 to 5% by weight. If the casein concentration is out of the above range, sufficient adhesiveness may not be imparted, or the composition may be gelated, making it difficult to apply it as a paint.

The complex may have a pH of 4 to 5. If the pH of the composition is out of the above range, a complex composition may not be formed. More specifically, casein exhibits low solubility in the range of pH 3.5 to 5.5, and acrylic monomers must be polymerized under such conditions to prepare a complex in which casein dissociated between acrylic polymers is bound. When polymerization is performed under conditions outside the above range, casein is liquefied, and interaction between the acrylic polymer and casein may not occur.

The composite may have a viscosity of 300 to 1,000 cps at 25 °C. If the viscosity is out of the above range, the paint may flow easily before drying, or it may be difficult to apply the paint.

The binder resin of the present invention contains an acid, which is to improve the water solubility of the binder resin. The acid is preferably a monovalent acid, and specifically, may be selected from the group consisting of acetic acid, nitric acid, hydrochloric acid, and mixtures thereof, preferably acetic acid. The acid may play a role of ionizing and dispersing the above-described amine group, and when the content exceeds the above range, the curing reaction rate slows down, whereas when the content is below the above range, the liquid phase may become opaque.

The inorganic solvent of the binder resin may include water, alcohol, ketone, etc., and it is preferable to use water in terms of environmental friendliness and workability. In the present invention, by using water instead of an organic solvent, it is environmentally friendly because it can exclude volatile organic compounds (VOCs) harmful to the human body, and has the advantage of being able to control a rapid exothermic reaction when organic substances are mixed.

In addition, when water is used as the inorganic solvent for the binder resin of the present invention, the water may include natural extracts of Bokryeong and Zucchini tree. The natural extract may be mixed with water in a weight ratio of 0.1:1 to 0.4:1 and used for the binder resin. If it is less than 0.1 by weight of water, the effect of the natural extract is insignificant, and if it is more than 0.4, problems with dispersibility and viscosity of the paint composition may appear. In the present invention, it is intended to impart the following effects to a coating film that can directly contact the skin through actions such as antibacterial, anti-inflammatory, and antioxidant by adding natural extracts of Bokryeong and Sulfur tree.

Poria cocos (Fr) Wolf may be Poria cocos (Fr) Wolf with a holey mushroom, and sometimes it may mean dried sclerotium of the above 　 Bokryeong. Bokryeong acts to inhibit contact dermatitis, including β-pachyman. Magnolia officinalis Rehd et Wils. is a deciduous tree that is native to China and is known to grow below 700m above sea level in the southern islands in Korea. Sulfur gourd is reported to have blood pressure lowering and relatively strong antibacterial activity, and major components of silver gourd include honokiol, magnolol, eudesmagnolol, magnoloside A, B, C, and magnocurarine.

The natural extracts of Bokryeong and Sulfur tree can be extracted through an extraction method under certain conditions in a state in which they are evenly mixed in a pulverized and dried form. The method for preparing a natural extract in the present invention may include the following steps.

a) mixing dried powder by pulverizing Bokryeong and Hwabak tree;

b) adding 80% (v/v) ethanol to the mixture and performing heat extraction at 60 to 80° C. for 8 hours;

c) separating the filtrate and residue by filtering the obtained extract;

d) adding purified water to the residue separated in step c) and ultrasonically treating the residue at 60 to 80° C. for 8 hours with continuous stirring using an ultrasonic extractor;

e) filtering the obtained extract to separate a filtrate and a residue; and

f) mixing the filtrate separated in steps d) and e);

According to one embodiment of the present invention, the bokryeong and silver basil trees of step a) may be mixed in a weight ratio of 1:1. In order to obtain functional effects of natural extracts, they are preferably mixed in the above weight ratio.

The inorganic powder of the coating composition may include 10 to 20 parts by weight of zeolite, 10 to 30 parts by weight of diatomaceous earth, and 20 to 50 parts by weight of a porous metal organic structure (MOF) based on the total weight of the binder resin.

Zeolite is used as a means to have multiple functions by using the pore structure and its unique physical properties and functional properties. Looking in detail, a 3-dimensional pore structure with a large surface area is suitably applied to the formation of a breathable sound-absorbing structure, resulting in excellent A means for expecting a soundproofing effect, a means for applying a catalyst, an ion exchange function, and an antibacterial function, a means for using a 3-dimensional pore structure to control the humidity of a coating film, and a means for adsorbing and deodorizing life odors such as ammonia. can be used as

The zeolite may include a material containing silicon (Si), aluminum (Al), and silver (Ag) atoms in a crystal lattice structure, as well as a material containing substitution elements for silicon, aluminum, and silver. That is, the zeolite may include a silver (Ag) ion component substituted on the surface or may be an amorphous silica alumina-zeolite composite. The particle diameter of this metallic zeolite may range from 1 to 5 μm.

These zeolites can implement antibacterial or antiviral effects in the following two ways. In the first method, when bacteria or fungi, which are cellular materials, are located near zeolite, metal ion components are easily dissociated and reach the cell membranes of bacteria and fungi by dispersion, and are adsorbed to proteins of the cell membranes and destroy the cell structure at the same time. causes the energy metabolism of bacteria and fungi to become inoperable and kills the bacteria themselves. As a second method, there is a sterilization action by active oxygen. Specifically, since it is manufactured using zeolite, which is a ceramic inorganic material, as a carrier and is composed of metal oxides such as SiO ₂ and Al ₂ O ₃ , oxygen bound to the skeleton structure is partially converted into active oxygen. Like the antibacterial metal, this active oxygen is adsorbed on the protein layer of the cell membrane of bacteria or fungi and exhibits a strong sterilization effect.

In addition to the silica and/or alumina substituted and included in the zeolite, the inorganic powder may further include 1 to 10 parts by weight of silica or alumina powder individually.

Silica (SiO ₂ ) may be added as a matting agent for increasing the flame retardancy of the coating film, and in this case, the average particle diameter of the silica nanoceramic particles is preferably in the range of 500 to 2000 nm. Alternatively, it may be added as a silver nano-silica composite in which silver nanoparticles of 1 to 5 nm are combined. The silver nano-silica composite exhibits a catalytic function even in the absence of light and has antibacterial and deodorizing functions, and the catalytic effect can be further increased when light or thermal energy is absorbed.

Alumina (Al ₂ O ₃ ) has high hardness and excellent strength and corrosion resistance. In addition, due to its high thermal stability, it is possible to maintain the durability of the paint for a long period of time by preventing the temperature rise of the adherend, reducing shrinkage and expansion, and preventing neutralization/chlorination. This effect appears when the average particle diameter of alumina nanoceramic particles is added in the range of 500 to 1500 nm, and ultrafine particle powder floats to the surface of the coating film during drying to form a dense and high hardness coating film.

Diatomaceous earth provides porosity to the surface of the coating film, controls gloss, and prevents cracks. Diatomaceous earth may be included in an amount of 10 to 30 parts by weight, and if less than 10 parts by weight, the porosity of the surface of the coating film may be insufficient, resulting in inferior antibacterial and antiviral functions, and insufficient gloss control and crack prevention effects. On the other hand, if it exceeds 30 parts by weight, crack prevention may be adversely affected.

In the present invention, by adding a porous metal organic framework (MOF), which has excellent antibacterial, deodorizing, and moisture absorption and desorption effects, as a main component of the inorganic powder, the strength and adhesion of the coating film are increased by reducing the addition amount of the remaining inorganic powders described above. It is characterized in that the inorganic powder is not smeared even after drying the coating film.

The porous metal organic structure may be included in an amount of 20 to 50 parts by weight, preferably 30 to 40 parts by weight, compared to the binder resin. It may be added in a compounding ratio (weight ratio) of 2 to 1:4.

Metal Organic Framework (MOF), a chemically robust and thermally stable nanomaterial, is used as a promising candidate in various application fields, and is one of the sub-family of metal organic frameworks with a sodalite zeolite-type structure. The phosphorus zeolite imidazolate framework (ZIF) has both large and small cavities. As such, the oxide product (Co ₃ O ₄ ) of ZIF-67 has permanent porosity, and carbon dots (CDs) and copper (Cu) can be deposited as a catalytically active material based on it.

Cobalt oxide (Co ₃ O ₄ ) of ZIF-67 structure is obtained from cobalt nitrate hexahydrate (Co(NO ₃ ) ₂ 6H ₂ O) and Hmim (1-Hexyl-3-methyl-imidazolium) using a co-precipitation method. Porous Co ₃ O ₄ can be synthesized by calcining the ZIF-67 metal organic structure. Specifically, in the co-precipitation method, cobalt nitrate hexahydrate and Hmim were dissolved in methanol, mixed and stirred, and the mixed solution was reacted for 20 hours or more, and the precipitate was centrifuged, washed, and dried to obtain a ZIF-67 metal-organic structure. You can get it. The obtained ZIF-67 structured cobalt oxide (Co ₃ O ₄ ) is dodecahedral and may have an average size ranging from 0.5 to 2.5 μm.

Cu/ZIF-67 was obtained by immersing the dodecahedron of cobalt oxide (Co ₃ O ₄ ) of the ZIF-67 structure in an ethanol solution containing Cu(NO ₃ ) ₂ and shaking the resulting suspension at room temperature for about 1 hour to obtain copper ions. (Cu ²⁺ ) can be incorporated into the ZIF-67 structure. Subsequently, Cu/ZIF-67 may be prepared by heat treatment at 400 to 500° C. to reduce copper ions (Cu ²⁺ ). At this time, the amount of the Cu nanoparticles combined by deposition may be 5 to 15% by weight, preferably 8 to 12% by weight, considering the yield of the manufacturing method and antibacterial / deodorizing ability.

Cu/ZIF-67 can provide antibacterial/deodorizing properties while preventing changes in the appearance of the coating film, such as color change due to the addition of copper, by binding copper atoms having antibacterial properties in the microporous structure.

CDs/ZIF-67 was deposited by mixing the cobalt oxide (Co ₃ O ₄ ) dodecahedron of the above-prepared ZIF-67 structure with carbon dots (CDs) and ethanol, and then ultrasonically dispersing, and then drying the CDs/ZIF. You can get -67. Here, carbon dots deposited and bonded to CDs/ZIF-67 may be nitrogen-doped carbon dots (N-doped CDs). Nitrogen-doped carbon dots can be synthesized by hydro-thermal carbonization using chitosan (CS) and acrylamide (AAM) as precursors of carbon dots. The mass ratio of chitosan and acrylamide may be in the range of 1:15 to 1:25, and the amount of carbon dots (CDs) bonded by deposition may be 5 to 10% by weight considering the yield of the manufacturing method.

CDs/ZIF- ₆₇ uses acrylamide, a superabsorbent polymer with strong hydrophilicity, as a raw material for carbon point synthesis _. OH), carboxylic acid (-COOH), amide (-CONH-), and primary amide (-CONH ₂ ). Accordingly, the coating composition of the present invention including CDs/ZIF-67 has excellent moisture absorption and desorption ability after forming a coating film, and can control indoor humidity and prevent dew condensation.

The binder resin and the inorganic powder may be mixed in a weight ratio of 100:70 to 100:90. In the present invention, by adding a CDs/ZIF-67 organometallic structure with excellent moisture absorptive and desorptive ability and a Cu/ZIF-67 organometallic structure with excellent antibacterial/deodorizing ability as main inorganic components, inorganic materials such as pigments and ceramics for functioning Compared to other paint compositions that are added in a significant amount, even a minimum amount of inorganic powder not only exhibits excellent effects, but also improves the strength and adhesion of the coating film. The evenly dispersed and painted coating composition can solve the problem of floating due to a large amount of inorganic materials and poor adhesion or staining of inorganic materials on the surface of the coating film even after drying.

In addition, the water-soluble paint composition according to the present invention may further include a thickener depending on painting characteristics and environment. The thickener can impart viscosity to the paint, improve the flowability of the paint composition through compatibility with inorganic powder, and improve workability during roller operation. For example, it may be prepared by including a thickener such as amide wax, organic clay, cellulose derivative, polyacrylic acid polymer, or urethane dispersant. Specifically, the thickener may be carboxymethylcellulose.

In addition, the water-soluble coating composition according to the present invention may further include organic bentonite, the aforementioned thickener, and the like as an anti-settling agent, and may further include antioxidants such as phenol-based, thioether-based, and phosphorus-based compounds.

In addition, another embodiment of the present invention is a painting method for interior architectural finishing using the water-soluble paint composition, comprising the steps of removing foreign substances attached to the surface of the surface to be coated; forming a finishing layer with a thickness of 0.3 to 0.5 mm by applying the water-soluble paint composition having excellent adhesion strength; and drying the finishing layer.

The step of removing the foreign substances attached to the surface of the surface to be installed may be performed by a suitable on-site treatment method such as high-pressure watering or grinding. Thereafter, the water-soluble coating composition may be uniformly mixed and applied to form a finishing layer having a thickness of 0.3 to 0.5 mm. It may be applied one or more times until reaching the above thickness range, and the finishing layer may be dried at room temperature for 48 hours or more.

The water-soluble coating composition of the present invention not only exhibits the above-described effects with a minimum amount of inorganic powder compared to other coating compositions in which a significant amount of inorganic materials are added, but also can improve the strength and adhesion strength of the coating film. Therefore, it is applied to the surface of not only wood, gypsum board, cement concrete, but also steel buildings with excellent adhesion even with a thin thickness, preventing defects such as lifting during subsequent work such as wallpapering work, and antibacterial activity even when used as a final coating film. It is harmless to the human body, eco-friendly, and can solve the problem of inorganic substances on the surface of the coating film.

Hereinafter, the present invention will be described in more detail through specific examples. The present invention is not limited to these embodiments.

<Preparation of binder resin>

As shown in Table 1 below, binder resins of Examples 1 to 3 were prepared. An acrylic polymer compound and a thermal polymerization initiator were added dropwise over 3 hours and maintained in the reactor for 3 hours. Thereafter, acetic acid and water were added and diluted to obtain a binder resin.

In Examples 4 and 5, casein-linked acrylic polymer compound complexes were prepared by introducing an aqueous casein solution having a concentration of 1 to 5% by weight into a reactor and adding ammonia water until the pH reached 8 to dissociate casein, and then acrylic acid saponified with ammonium salt. A monomer, methyl methacrylate (MMA), and ammonium peroxide sulfate were added and reacted. After completion of the reaction, a PAA-casein complex in which dissociated casein was bound to the surface of the polyacrylic acid particle was obtained. Thereafter, acetic acid and water were added and diluted to obtain a binder resin. At this time, the PAA-casein complexes of Examples 4 and 5 had pHs of 4.4 and 4.5, respectively, and 25° C. viscosities in the range of 370 to 800 cps.

division Example 1 Example 2 Example 3 Example 4 Example 5 casein concentration - - - 2% by weight 4% by weight acrylic
polymer
compound PAA-casein complex - - - 80 80 MMA 60 60 60 20 20 DMAEMA 20 DEAEMA 20 20 AAM 20 N-BMAA 20 N-HEAAs 20 initiator 1.2 1.2 1.2 1.5 1.5 acetic acid 7 7 7 5 5 water 60 60 60 45 45 Natural extracts - 20 20 - 15

The initiator, acetic acid, water, and natural extract in Table 1 represent parts by weight based on 100 parts by weight of the acrylic polymer compound.

Manufacture of natural extracts

Sulfur tree (peel) was washed clean, dried after removing water, and pulverized into 1 to 3 cm with a grinder along with Bokryeong of dried crude medicine, and then mixed at a weight ratio of 1: 1 and mixed evenly. 10 L of 80% (v/v) ethanol was added to 1 kg of the mixture, and extraction was performed at 60 to 80° C. for 8 hours. After filtering the obtained extract and separating the filtrate and the transcript, the filtrate (first filtrate) was stored separately. In addition, purified water was added to the separated residue, ultrasonic treatment was performed while continuously stirring at 60 to 80 ° C. for 8 hours using an ultrasonic extractor, and the sonicated extract was filtered to obtain a filtrate (second filtrate) and It was isolated as a residue. Then, after mixing the first filtrate and the second filtrate, concentrated under reduced pressure and lyophilized to prepare a natural extract. The prepared natural extracts were further added to Examples 2, 3 and 5 of Table 1 above.

<Preparation of inorganic powder>

Synthesis of porous ZIF-67 metal-organic structure

ZIF-67 nanoparticles were synthesized using a simple and facile co-precipitation method. 2.912 g Co(NO ₃ ) ₂ 6H ₂ O and 6.568 g Hmim (1-Hexyl-3-methyl-imidazolium) were each dissolved in 200 mL methanol. Both solutions were magnetically stirred for 5 minutes to completely dissolve the powder. The solutions were then mixed together and stirred continuously at 200 rpm for 1 hour at room temperature (25° C.). After the reaction, the purple precipitate was collected, centrifuged at 6000 rpm for 10 minutes, and washed with ethanol three times. The purified product was dried in an oven at 60 ° C. for 12 hours to create a ZIF-67 template, and the synthesized ZIF-67 was placed in a ceramic crucible and pyrolyzed at 400 ° C. to obtain porous ZIF-67 Co ₃ from which organic residues were removed. A metal oxide of O ₄ was obtained.

The obtained porous ZIF-67 Co ₃ O ₄ had a specific surface area of 8.197 m ² /g and an average pore size of 33.522 nm.

carbon point synthesis

N-doped CDs were synthesized by hydro-thermal carbonization using chitosan (CS) and acrylamide (AAM) as precursors of carbon dots. First, chitosan (CS) and acrylamide (AAM) were dissolved in 20 mL of deionized water with continuous stirring at a mass ratio of 1:20. For the hydrothermal reaction of the mixed solution, after transferring to a stainless steel autoclave equipped with Teflon and reacting at 220 ° C. for 12 hours, the precipitate of the dark brown product solution was removed by centrifugation, and the brown supernatant was filtered through a 0.22 mm membrane. After dialysis against deionized water, N-doped CDs were obtained by lyophilization.

Manufacturing of CDs/ZIF-67 and Cu/ZIF-67

The synthesized carbon dots (N-doped CDs) and metal oxides of porous ZIF-67 Co ₃ O ₄ were mixed in 90% trace amount of ethanol, sonicated for 1 minute to completely disperse, and then dried to obtain CDs/ZIF-67 metal organic compounds. got a struct. The carbon dots deposited in the porous ZIF-67 structure was measured at 7.5 wt%.

In addition, the metal oxide of porous ZIF-67 Co ₃ O ₄ was mixed with an ethanol solution containing Cu(NO ₃ ) ₂ and the resulting suspension was shaken at room temperature for 1 hour to integrate Cu ²⁺ ions into ZIF-67. Subsequently, ZIF-67 was heat-treated at 450° C. to prevent carbonization, thereby reducing Cu ²⁺ to Cu ⁰ and obtaining Cu/ZIF-67. Deposited Cu atoms in the porous ZIF-67 structure measured 9.82 wt%.

Inorganic powder was prepared by mixing zeolite and diatomaceous earth together with the prepared CDs/ZIF-67 and Cu/ZIF-67 metal organic structures as shown in Table 2 below. Zeolite was added as a silica alumina-zeolite composite, and a portion of silica and/or alumina nanoceramic powder was additionally mixed.

Comparative Examples 1 and 2 were aimed at existing antibacterial/deodorizing paint compositions that did not contain metal organic structures and added a large amount of inorganic materials in a ratio of 1:0.9 to 1:1.3 to binder resin.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 zeolite 12 15 12 15 12 20 20 diatomaceous earth 20 20 20 20 20 20 10 Cu/ZIF-67 10/40 10/35 10/40 10/40 10/45 CDs/ZIF-67 30/40 25/35 30/40 30/40 35/45 silica 5 5 5 - 5 20 20 alumina - 5 5 10 5 - 10 calcium carbonate talc
titanium dioxide
magnesium oxide 50 60 Total 77 80 82 85 87 110 120

The numerical values in Table 2 represent parts by weight based on 100 parts by weight of the binder resin.

<Evaluation of physical properties>

Adhesion and adhesion strength

Adhesion was performed according to the KS M ISO 2409:2013 method. After making 100 checkerboard eyes by drawing 11 horizontal and vertical lines at 1 mm intervals using a knife on the painted surface of the test specimen, cellophane tape was attached and peeling was observed. It was evaluated on a scale of 0 to 5 according to the surface state of the crosscut area where flaking occurred.

0: no exfoliated checkerboard grid

1: A small piece of the coating peels off at the intersection of the cutting line. within 5%

2: Peeling into small pieces along the incisal plane and/or at the intersection of the incisal lines. 5-15%

3: Partial or all peeling along the cut surface. 15-35%

4: All of a part of the checkerboard grid peeled off. 35-65%

5: 0 to 4 N/A

The adhesion strength was performed by the KS F 4715:2007 method, which is an evaluation method for wall coating materials for thin finishing.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 adhesiveness 0 0 0 0 0 One 2 Standard State Bonding Strength
(N/㎟) 1.2 1.1 1.1 1.3 1.2 1.0 1.0 Adhesion strength after immersion
(N/㎟) 0.9 0.9 0.9 1.0 1.0 0.6 0.5

As shown in Table 3, the water-soluble paint composition according to the embodiment of the present invention showed excellent adhesion after forming a coating film and adhesion strength in a standard state/after immersion. On the other hand, it was confirmed that Comparative Examples 1 and 2, which did not contain the metal organic structure, which is a strong moisture absorption and release material, and contained a large amount of inorganic materials, had somewhat insufficient adhesion and showed inferior adhesion strength.

Antimicrobial and antifungal resistance

In order to meet the antibacterial and antifungal resistance quality standards of the interior finishing painting work of buildings, the antibacterial reduction rate and antibacterial activity value were evaluated after 24 hours in a 5cm × 5cm test piece according to the JIS Z 2801:2012 method, and the antifungal resistance was It was evaluated after culturing for 28 days at a relative humidity (92.8 ± 2.0)% and a temperature (28 ± 0.2) ° C according to the ASTM D 6329-98 (2015) method.

Strain 1: Staphylococcus aureus ATCC 6538P

Strain 2: Escherichia coli A8739

Strain 3: Aspergillus brasiliensis ATCC 9642

division Example 1 Example 2 Example 3 Example 4 Example 5 antibacterial Decrease rate (%) strain 1 >99% >99% >99% >99% >99% strain 2 >99% >99% >99% >99% >99% antibacterial activity 5.8 6.1 6.0 5.7 6.1 antifungal
resistance spore count
(CFU/plate) strain 3 <10 <10 <10 <10 <10 Log (CFU) 1.0 1.0 1.0 1.0 1.0

The water-soluble coating composition according to the embodiment of the present invention showed a bacteriostatic reduction rate of 99% or more for both Staphylococcus aureus and Escherichia coli and an antibacterial activity value exceeding 2.0, which was confirmed to be suitable for quality standards with excellent antibacterial properties. In addition, since mold did not grow, the anti-fungal resistance also met the quality standards of the health-friendly housing construction standards (Notice No. 2016-1084 of the Ministry of Land, Infrastructure and Transport).

Evaluation of deodorization and absorption of VOCs

The absorption capacity of odor and volatile organic compounds (VOCs) was evaluated using the test method of the detector tube type gas meter of KS I 2218:2009. After putting 100 ppm of gas into the 2L chamber, the deodorization rate was measured over 30, 60, 90, and 120 minutes.

division Black
Concentration (ppm) Example 3 Example 4 gas elapsed time
(min) Concentration (ppm) Deodorization rate (%) Concentration (ppm) Deodorization rate (%) ammonia 0 100 100 - 100 - 30 93 32 68 37 63 60 90 14 86 15 85 90 87 3 97 2 98 120 85 0 100 0 100 trimethylamine 0 100 100 - 100 - 30 99 71 29 73 27 60 97 53 47 54 46 90 94 39 61 39 61 120 93 31 69 32 68 formaldehyde 0 100 100 - 100 - 30 94 41 59 38 62 60 93 33 67 31 69 90 91 25 75 26 74 120 90 19 81 22 78 xylene 0 100 100 - 100 - 30 98 61 39 60 40 60 97 49 51 44 56 90 95 33 67 31 69 120 94 19 81 17 83

Examples 3 and 4 of the present invention, which contain CDs/ZIF-67 and Cu/ZIF-67 metal organic structures with excellent deodorization and adsorption capabilities, as main components along with zeolite and diatomaceous earth, which are porous inorganic materials, have excellent deodorization and volatile organic compounds Adsorption capacity was shown.

Moisture absorption/desorption evaluation

The amount of moisture absorption and release was measured by the KS F 2611 method, which is a test method for moisture absorption and release of building materials.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Moisture Absorption (g/㎡) 74 71 75 77 83 57 54 Moisture release (g/㎡) 57 56 58 60 63 40 39

As can be seen in Table 6, the water-soluble paint composition and the coated film according to the embodiment of the present invention contain CDs/ZIF-67 metal organic structures containing carbon points that are excellent for moisture absorption and desorption. was found to have In particular, Example 5, which further included CDs/ZIF-67, showed very good moisture absorption and desorption. On the other hand, Comparative Examples 1 and 2 absorbed and released a certain amount of moisture through porous zeolite and diatomaceous earth, but it was confirmed that it was insufficient.

Various embodiments described above may be embodied in other specific forms without departing from their technical ideas and essential characteristics. Accordingly, the above detailed description should not be construed as limiting in all respects and should be considered illustrative. The scope of the various embodiments should be determined by a reasonable interpretation of the appended claims, and all changes within the equivalent scope of the various embodiments are included in the scope of the various embodiments. In addition, claims that do not have an explicit citation relationship in the claims may be combined to form an embodiment or may be included as new claims by amendment after filing.

Claims (6)

A binder resin containing an acrylic polymer compound, an inorganic solvent, a thermal polymerization initiator, and an acid; and
Inorganic powders including silica, zeolite, diatomaceous earth and porous metal organic structures (MOFs);
The acrylic polymer compound is an acrylic polymer compound having an amine group or a complex in which dissociated casein is bonded to at least a part of the surface of the acrylic polymer particle,
The porous metal organic structure is Cu / ZIF-67 in which copper is vapor-bonded and CDs / ZIF-67 in which carbon dots are vapor-bonded,
The Cu/ZIF-67 and CDs/ZIF-67 are added in a weight ratio of 1:2 to 1:4,
The copper (Cu) particles deposited on the Cu / ZIF-67 are 5 to 15% by weight,
The carbon point deposited on the CDs / ZIF-67 is 5 to 10% by weight of a water-soluble coating composition with excellent adhesion strength.
According to claim 1,
The binder resin,
A water-soluble coating composition having excellent adhesion strength, comprising 100 parts by weight of an acrylic polymer compound, 40 to 80 parts by weight of an inorganic solvent, 1 to 10 parts by weight of a thermal polymerization initiator, and 5 to 10 parts by weight of an acid.
According to claim 1,
The inorganic powder,
10 to 20 parts by weight of zeolite, 10 to 30 parts by weight of diatomaceous earth and 20 to 50 parts by weight of a porous metal organic structure (MOF) based on the total weight of the binder resin,
A water-soluble coating composition having excellent adhesion strength in which the blending weight ratio of the binder resin and the inorganic powder is 100:70 to 100:90.
delete delete A painting method for interior architectural finishing using the water-soluble paint composition according to any one of claims 1 to 3,
removing foreign matter adhering to the surface of the surface to be coated; forming a finishing layer with a thickness of 0.3 to 0.5 mm by applying the water-soluble paint composition having excellent adhesion strength; and drying the finishing layer.