KR20210155049A - Antifouling paint composition comprising mono-dispersed spherical mesoporous silica impregnated nano silver particles - Google Patents

Abstract

The present invention relates to an antifouling paint composition comprising spherical mesoporous silica containing dispersed silver nanoparticles. The antifouling paint composition, to which spherical mesoporous silica containing dispersed silver nanoparticles according to the present invention has been applied, imparts an excellent antifouling effect to painted surfaces such as a hull, and the like, by blocking the biofilm generation, thereby being highly effective in contributing to the protection of the ecosystem.

Description

Antifouling paint composition comprising mono-dispersed spherical mesoporous silica impregnated nano silver particles

The present invention relates to an antifouling paint composition, and more particularly, to an antifouling paint composition that does not leak silver nanoparticles, that is, an antifouling paint composition comprising a structure dispersed inside the pores of spherical mesoporous silica and not leaking externally. .

Antifouling paints for ships to protect ship hulls from foreign substances such as marine organisms have been developed in various forms. In particular, the part below the waterline where the hull is submerged in seawater will be attached to various kinds of animal and vegetable marine life. The adhesion of these foreign substances causes an increase in fuel consumption and a decrease in sailing speed due to an increase in resistance applied to the hull during operation. Due to these problems, shipping companies, engine manufacturers, shipyards, and paint industries are making continuous efforts to suppress the adhesion of marine organisms to ships and the like. In addition, in the reality that fuel consumption increases exponentially due to the recent increase in size and speed of ships, the demand for solving these problems is further increasing.

Conventionally, the form of adding a tin compound as an antifouling paint to solve the above problem has been used most. These antifouling paints are inexpensive, easy to handle, and have excellent antifouling performance. However, as tin compounds are known to be a major cause of marine pollution releasing environmental hormones, their use is limited. A form newly developed recently is a self-abrasion type antifouling paint that exhibits antifouling performance by using the principle that the antifouling paint film gradually wears out during the sailing of a ship instead of a tin compound. The self-abrasive antifouling paint does not emit environmental hormones, but the strength of the paint film is weak, so it must be frequently repaired and painted, and the paint film itself has poor antifouling performance. have.

Silver is a substance that directly or indirectly exerts antibacterial and sterilizing effects. Directly, as δ ⁺ ions are involved in cell death due to cell membrane destruction, δ ⁺ ions block cell functions or destroy cell membranes by binding to -SH, -COOH, and -OH of cells. It exhibits antibacterial and sterilizing effects. In addition, indirectly, δ ⁺ ions released from silver act as a catalyst for oxygen, thereby changing oxygen in the air into active oxygen, and the active oxygen exerts sterilization and antibacterial effects. A number of inventions utilizing this property of silver have been disclosed. Korean Patent Publication No. 2010-0130307 discloses a solvent-free epoxy paint composition containing liquid silver nanoparticles, that is, uniformly disperses silver nanoparticles in the paint to improve antibacterial and sterilization functions, Disclosed are a paint capable of spray painting on the inner surface of a water pipe and a drinking water tank, and a method for manufacturing the same. Since the solvent-free epoxy paint composition according to the invention disclosed in the above patent contains liquid silver nanoparticles, it can be uniformly dispersed in the paint. As a result, since the silver nanoparticles are uniformly distributed even in the coated paint layer, the antibacterial and sterilization functions of the silver nanoparticles can be further improved. Silver nanoparticles with a size of 5 to 10 nm contained in liquid silver nanoparticles have a minimum inhibitory concentration (MIC) as low as 10 ppm, so a high antibacterial and sterilization effect can be expected by using a small amount. And the solvent-free epoxy paint composition according to the present invention can be used as a paint for spray painting without a diluent by lowering the viscosity of the paint by using a castor oil derivative flow inhibitor that is activated at 40 to 50° C. as a sensitizer.

However, as a lot of research results on the harmfulness of silver nanomaterials have recently come out, the invention of Korean Patent Application Laid-Open No. 2010-0130307 has a problem of harmfulness. According to Nanotoxicology (Volume 10, 2016 - Issue 5), a toxicology-related journal, due to its antibacterial properties, if the amount of 'silver nanoparticles' used in daily life exceeds a certain amount, it can threaten the aquatic ecosystem, and the chronic It discloses that the results have been obtained that the concentration of silver nanoparticles should be less than 0.614 μg/L to protect aquatic organisms from exposure. In this paper, an experiment was conducted to evaluate the chronic toxicity of silver nanoparticles on 6 aquatic organisms such as algae, euglena, crustaceans, and fish, and whether there is any problem in growth and development, and activity in water (swimming) ) was evaluated to see if there was any problem with reproduction or not. As a result, it is disclosed that all six species were observed to be affected by the toxicity due to the silver nanomaterial. Based on these results, the research team applied the 'High Reliability Environmental Guideline Value Calculation Methodology' and analyzed. As a result, the concentration that can protect 95% of aquatic species in case of chronic exposure to silver nanomaterials is 0.614 μg per 1L. .

Therefore, there is a strong demand for the development of a paint for ships that has an antifouling function while silver particles, particularly silver nanomaterials, do not leak into the ocean.

An object of the present invention is to provide an antifouling paint composition that does not leak silver nanoparticles, that is, an antifouling paint composition that includes a structure that is dispersed inside the pores of spherical mesoporous silica and does not leak externally.

Silver nano antifouling paint according to the present invention for achieving the above technical problem

An antifouling paint produced by mixing an antifouling agent, a solvent, a pigment and an additive in a resin substrate, the antifouling agent is characterized in that it is formed of spherical mesoporous silica 100 containing silver nanoparticles dispersed therein.

Preferably, the spherical mesoporous silica 100 in which the silver nanoparticles are dispersed may include silica particles; a plurality of pores formed on the surface and inside of the silica particles; and silver nanoparticles (200) dispersed and contained within the pores.

More preferably, the diameter of the silica particles is 100-500 nm, the diameter of the pores is 1-2 nm, and the diameter of the silver nanoparticles 200 is 2-5 nm.

More preferably, the silica particles,

Tetraethoxyorthosilicate (TEOS), Tetramethoxyorthosilicate (TMOS), Tetraprocoxyorthosilicate (TPOS), Tetrabutoxyorthosilicate (TBOS), Tetratoxyorrosilicate (TPEOS), Tetra It is characterized in that at least one of (methylethylketooxymo)silane, vinyloxymosilane (VOS), phenyltris(butanoneoxime)silane (POS) and methyloxymosilane (MOS) is used as a precursor.

Preferably, the resin is at least one of a phenol resin, an alkyd resin, a silicone alkyd resin, a silicone resin, an epoxy ester resin, a chlorinated rubber resin, a vinyl chloride resin, an epoxy resin, a polyurethane resin, a silicone acrylic resin, and a fluorine resin. characterized in that

Preferably, the solvent is characterized in that at least one of xylene, ethylbenzene, n-butyl acetate, toluene, acetone, MEK, Butyl Cellosolve 2-Butoxyethanol and Ethyl Cellosolve 2-Ethoxyethanol is used. do.

Preferably, the pigment is an inorganic pigment or an organic pigment.

More preferably, the inorganic pigment comprises ferric oxide red, zinc oxide, or a mixture thereof.

Preferably, 20 to 30 parts by weight of the resin, 25 to 40 parts by weight of the solvent, 10 to 30 parts by weight of the pigment, 1 to 5 parts by weight of the additive, and 10 to 30 parts by weight of the antifouling agent are mixed. characterized in that

The antifouling paint composition comprising the spherical mesoporous silica 100 containing silver nanoparticles dispersed in accordance with the present invention prevents and eliminates the formation of a Bao film layer on the paint application surface of a ship, etc., thereby preventing contamination of the paint application surface. There is an excellent effect of preventing, and there is no direct leakage of the silver nanoparticles 200, thereby preventing marine pollution.

1 is a view showing a cross-section of spherical mesoporous silica containing silver nanoparticles dispersed therein.

Additional objects, features and advantages of the present invention may be more clearly understood from the following detailed description and accompanying drawings.

Prior to the detailed description of the present invention, the present invention can make various changes and can have various embodiments, and the examples described below and shown in the drawings are not intended to limit the present invention to specific embodiments. No, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

When an element is referred to as being “connected” or “connected” to another element, it is understood that it may be directly connected or connected to the other element, but other elements may exist in between. it should be On the other hand, when it is said that a certain element is "directly connected" or "directly connected" to another element, it should be understood that the other element does not exist in the middle.

The terms used herein are used only to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

In addition, terms such as "...unit", "...unit", "...module", etc. described in the specification mean a unit that processes at least one function or operation, which includes hardware or software or hardware and It can be implemented by a combination of software.

In addition, in the description with reference to the accompanying drawings, the same components are given the same reference numerals regardless of the reference numerals, and the overlapping description thereof will be omitted. In describing the present invention, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

The antifouling paint composition comprising the spherical mesoporous silica 100 containing silver nanoparticles dispersed in accordance with the present invention for achieving the above technical problem is produced by mixing an antifouling agent, a solvent, a pigment and an additive in a resin substrate As an antifouling paint,

The antifouling agent is characterized in that it is formed of spherical mesoporous silica 100 containing silver nanoparticles dispersed therein.

Paints are generally composed of resins, pigments, solvents and additives. In the case of antifouling paint, an antifouling agent is added here. In the present invention, it is characterized in that it contains an antifouling agent formed of spherical mesoporous silica 100 in which silver nanoparticles are dispersed.

Silver (Ag) is widely known to have antibacterial and bactericidal effects.

The direct antibacterial and bactericidal effects of silver can be divided into two categories. Silver can be directly involved in cell death by destroying the cell membrane in the ionic form (Ag+). In addition, silver ions combine with -SH, -COOH, and -OH of cells to block cell functions or destroy cell membranes, which eventually results in antibacterial and sterilizing effects.

Silver also has an indirect antibacterial and bactericidal effect. It acts as a catalyst through the release of supersaturated oxygen. Specifically, it is a mechanism by which the released silver ions act as oxygen and catalyst to change oxygen in the air into active oxygen, and this active oxygen exerts sterilization and antibacterial effects.

Since it is a feature of the present invention to exhibit an antibacterial and sterilizing effect without leakage of the silver nano material, it is essential to check whether the silver nano material is leaked through a physical desorption test. As a result of measuring spherical mesoporous silica containing nanoparticles dispersed in the sample after 1 hour of ultrasonication and 1 hour of centrifugation, no leaked silver nanomaterials were found.

In addition, by performing a boiling desorption test, silver nanomaterials were not detected even after boiling a spherical mesoporous silica sample containing nanoparticles dispersedly at 95°C for 1 hour.

By grafting nanotechnology, SNT+AgNP inclusion technology, spherical mesoporous silica 100 containing silver nanoparticles dispersed was prepared.

There is no outflow of organic compounds, inorganic compounds or nanoparticles from the mesoporous silica. Pure superoxide anion is generated by the conversion of dissolved oxygen in water, and this has the characteristic of expressing antibacterial and antiviral functions without generating resistant bacteria.

The manufacturing process of the spherical mesoporous silica 100 in which silver nanoparticles are dispersed is as follows.

As the template (organic template) used for nanostructure synthesis is removed, *?* nanopores with a diameter of 2 nm are created in the space occupied by the *?* template. Silica has a large specific surface area and allows the flow of fluids (water and air) through the nanopores, thereby facilitating the movement of fluids into the structure. A state in which the indirect sterilization effect (the effect of oxygen molecules catalyzing with the silver nano surface to become supersaturated oxygen with strong sterilizing power against bacteria) is optimally achieved by the silver nanoparticles encapsulated in the pores. .

The spherical mesoporous silica 100 containing silver nanoparticles dispersedly contained as part of the composition in the present invention is disclosed in Republic of Korea Patent No. 1333007 (Method for producing spherical mesoporous silica containing silver nanoparticles dispersed). is a product Accordingly, the contents related to the spherical mesoporous silica 100 in which the silver nanoparticles are dispersedly contained in the claims 2 to 12 are described in detail in the Korean Patent Registration No. 1133007.

Nanostructures (structures in which the size of particles are micro-sized while having a nanostructure that exerts a nano effect*? Because it is a material (nano*?*structured materials), it is possible to solve the problem of harm to the human body of nanoparticles.

Nanoparticles are particles with a size of 1 to 100 nm, and a nanostructure material is a *?* material having a nanostructure with a size of 1-100 nm.

Preferably, the spherical mesoporous silica 100 in which the silver nanoparticles are dispersed may include silica particles; a plurality of pores formed on the surface and inside of the silica particles; and silver nanoparticles (200) dispersed and contained within the pores.

3 shows a cross section of the spherical mesoporous silica 100 containing silver nanoparticles dispersedly, and shows a route in which normal oxygen is converted into supersaturated oxygen through a silver catalyst in the pores of the silica.

Since the silver nanoparticles manufactured by the bottoms-up method are encapsulated, there is no risk of physical leaching out, thus solving the harmful effects of silver nanoparticles.

Since the main agent of the antibacterial action is supersaturated oxygen generated by the catalysis of silver nano-metal particles (Ag ^{0 ), not silver ions (Ag +} ) or silver nanoparticles (Ag ^{0 ) itself, it blocks the elution of silver ions} In addition to securing sustainability, it became possible to be free from environmental pollution problems caused by silver ion leakage raised by the US EPA (Insecticide and Rodenticide Act).

_{Since it is a pure natural mineral component (SiO 2} , Ag ⁰ ) antibacterial agent that does not contain chlorine-based and phenol-based antibacterial components harmful to the human body, it is possible to solve problems such as resistant bacteria (super bacteria).

Antifoaming agents, desiccants, antioxidants, dispersants, precipitation inhibitors and other various additives are used to improve the physical properties of the paint. Additives are indispensable elements that improve various properties of paints.

More preferably, the diameter of the silica particles is 100-500 nm, the diameter of the pores is 1-2 nm, and the diameter of the silver nanoparticles 200 is 2-5 nm. As described above, the silica particles having an antifouling function are not in a state in which nanoparticles are exposed, but are microparticle-sized nanostructures in which silver nanoparticles are included, so it is possible to solve the problem of harmfulness to the human body of nanoparticles, silica If the particle size is less than 100 nm, it still has harmful effects as fine particles. When the size of the silica particles exceeds 500 nm, it is difficult for the silica particles to be uniformly dispersed in the coating composition, and it is difficult to penetrate the silver nanoparticles into the pores of the interior, so that it is difficult to sufficiently enclose the silver nanoparticles in the pores. The size of the silver nanoparticles is 2 to 5 nm. In order for the silver nanoparticles to stably settle in the pores of the silica particles, the diameter of the pores is preferably 1 to 2 nm.

More preferably, the silica particles,

Tetraethoxyorthosilicate (TEOS), Tetramethoxyorthosilicate (TMOS), Tetraprocoxyorthosilicate (TPOS), Tetrabutoxyorthosilicate (TBOS), Tetratoxyorrosilicate (TPEOS), Tetra It is characterized in that at least one of (methylethylketooxymo)silane, vinyloxymosilane (VOS), phenyltris(butanoneoxime)silane (POS) and methyloxymosilane (MOS) is used as a precursor.

Preferably, the resin is at least one of a phenol resin, an alkyd resin, a silicone alkyd resin, a silicone resin, an epoxy ester resin, a chlorinated rubber resin, a vinyl chloride resin, an epoxy resin, a polyurethane resin, a silicone acrylic resin, and a fluorine resin. characterized in that

Various resins used for paint are also applicable to the antifouling paint of the present invention. When mixing each composition, the resin component must be completely dissolved in the solvent used. Incomplete dissolution causes non-uniformity of the coating film, which causes a problem in the coating film quality.

Preferably, the solvent is characterized in that at least one of xylene, ethylbenzene, n-butyl acetate, toluene, acetone, MEK, Butyl Cellosolve 2-Butoxyethanol and Ethyl Cellosolve 2-Ethoxyethanol is used. do.

Preferably, the pigment is an inorganic pigment or an organic pigment.

The function of the pigment used in the composition of the antifouling paint is to secure the coloration and durability of the coating film and the oiliness. For this purpose, various inorganic and organic pigments are widely used and sometimes mixed.

More preferably, the inorganic pigment comprises ferric oxide red, zinc oxide, or a mixture thereof.

It is more preferable to use a mixture of two inorganic pigments including ferric oxide red to implement a red antifouling paint and zinc oxide to secure the durability of the coating film.

Preferably, 20 to 30 parts by weight of the resin, 25 to 40 parts by weight of the solvent, 10 to 30 parts by weight of the pigment, 1 to 5 parts by weight of the additive, and 10 to 30 parts by weight of the antifouling agent are mixed. characterized in that

If the resin exceeds 30 parts by weight, it is not easy to apply due to poor flowability, and if it is less than 20 parts by weight, it flows down from the surface after application, thereby impairing the uniformity of the coated surface and the durability of the coating film. When the resin is used as the antifouling paint composition of the present application, it is preferable to use the above content in order to harmonize both durability and adhesion to the undercoat in the object to be coated. If the solvent exceeds 40 parts by weight, the anti-sagging of the paint is lowered, which can cause paint defects, cause a problem of dripping from the surface after application, and accelerate environmental pollution due to excessive use of volatile substances. A problem arises. On the other hand, if the content of the solvent is less than 25 parts by weight, the viscosity of the paint is high, so that it is difficult to secure coating workability. When the amount of the pigment exceeds 30 parts by weight, the strength of the coating film is impaired, and when it is less than 10 parts by weight, the color of the paint surface cannot be properly expressed, thereby causing a non-uniform color surface. When the additive exceeds 5 parts by weight, the strength of the coating film is lowered, and when it is less than 1 part by weight, there is a problem in that the additive cannot perform its functions. When the antifouling agent exceeds 30 parts by weight, in addition to the problem of cost increase, no more antifouling effect can be expected, and in the case of less than 10 parts by weight, the antifouling effect is insignificant.

100: spherical mesoporous silica containing silver nanoparticles dispersed
200: silver nanoparticles

Claims (9)

As an antifouling paint produced by mixing an antifouling agent, a solvent, a pigment and an additive with a base material,
The antifouling agent is silver nano antifouling paint, characterized in that it is formed of spherical mesoporous silica containing silver nanoparticles dispersed therein. According to claim 1,
The spherical mesoporous silica in which the silver nanoparticles are dispersed,
silica particles;
a plurality of pores formed on the surface and inside of the silica particles; and
Silver nano antifouling paint, characterized in that it is composed of silver nanoparticles dispersed inside the pores. 3. The method of claim 2,
The diameter of the silica particles is 100-500 nm,
The diameter of the pores is 1-2 nm,
The silver nano-antifouling paint, characterized in that the diameter of the silver nanoparticles is 2-5 nm. 3. The method of claim 2,
The silica particles are
Tetraethoxyorthosilicate (TEOS), Tetramethoxyorthosilicate (TMOS), Tetraprocoxyorthosilicate (TPOS), Tetrabutoxyorthosilicate (TBOS), Tetratoxyorrosilicate (TPEOS), Tetra A silver nano antifouling paint comprising at least one of (methylethylketooxymo)silane, vinyloxymosilane (VOS), phenyltris(butanoneoxime)silane (POS) and methyloxymosilane (MOS) as a precursor. According to claim 1,
The resin is characterized in that at least one of a phenol resin, an alkyd resin, a silicone alkyd resin, a silicone resin, an epoxy ester resin, a chlorinated rubber resin, a vinyl chloride resin, an epoxy resin, a polyurethane resin, a silicone acrylic resin, and a fluorine resin is used. silver nano antifouling paint. According to claim 1,
The solvent is a silver nano antifouling paint, characterized in that at least one of xylene, ethylbenzene, n-butyl acetate, toluene, acetone, MEK, Butyl Cellosolve 2-Butoxyethanol and Ethyl Cellosolve 2-Ethoxyethanol is used. . According to claim 1,
The silver nano antifouling paint, characterized in that the pigment is an inorganic pigment or an organic pigment. 8. The method of claim 7,
The inorganic pigment is silver nano antifouling paint, characterized in that it comprises ferric oxide red, zinc oxide, or a mixture thereof. According to claim 1,
20 to 30 parts by weight of the resin, 25 to 40 parts by weight of the solvent, 10 to 30 parts by weight of the pigment, 1 to 5 parts by weight of the additive, and 10 to 30 parts by weight of the antifouling agent are mixed silver nano antifouling paint.

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