WO2019160367A1

WO2019160367A1 - Crystalline molecular sieve-coated bead complex and article comprising same

Info

Publication number: WO2019160367A1
Application number: PCT/KR2019/001844
Authority: WO
Inventors: 윤영민
Original assignee: 주식회사 지오엔
Priority date: 2018-02-14
Filing date: 2019-02-14
Publication date: 2019-08-22
Also published as: KR20190098729A; KR102241264B1

Abstract

The present invention relates to a bead complex coated with a crystalline molecular sieve via chemical bonding, various articles comprising the bead complex, and a method for manufacturing the bead complex.

Description

Molecular Sieve Crystal Particle-Coated Bead Composites and Articles Containing the Bead Composites

The present application relates to bead complexes in which molecular sieve crystal particles are coated via chemical bonding, various articles containing the bead complexes, and methods of making the bead complexes.

Zeolites and the like are generally present as fine powders. In order to effectively utilize them, studies have been actively conducted to attach molecular sieve particles in the form of fine powders to the bead surface.

The simplest method was to immerse the beads in a turbid solution made of zeolite crystals and attach the zeolite particles by physical attraction between the surface of the zeolite and the surface of the beads [L. C. Boudreau, J. A. Kuck, M. Tsapatsis, J. Membr. Sci. 1999, 152, 41-59. This method is to control the degree of dispersion of the zeolite by controlling the rate of removing the zeolite from the turbidity, so it is difficult to form a uniform monolayer film of the zeolite particles. It tended to break away easily.

However, in the conventional methods, since the zeolite is attached to the beads (fabric) by a chemical method, a treatment cost according to the design of a separate process for this is required, and a process addition and a process may be performed separately from the fabric processing process. There was a problem that the process efficiency decreases over time. Accordingly, there is still a need for development of a method for stably coating molecular sieves on various bead surfaces.

The present application provides bead complexes in which molecular sieve crystal grains are coated via chemical bonding, various articles containing the bead complexes, and methods of making the bead complexes.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present disclosure provides bead complexes comprising molecular sieve crystal particles coated via chemical bonds to the surface of the beads.

A second aspect of the present disclosure provides an article comprising the bead composite according to the first aspect of the present disclosure.

A third aspect of the present application provides a method for preparing a bead complex according to the first aspect of the present application, comprising coating the molecular sieve crystal particles on the surface of the beads to chemically bond the molecular sieve crystal particles to the surface of the beads. to provide.

According to the embodiments of the present disclosure, a bead complex stably coated on surfaces of beads having molecular sieve crystal particles having various shapes and / or various colors may be provided, and the bead complex may be used to provide various articles. .

According to embodiments herein, an article that is a container containing a liquid, a semi-liquid, or a gel, comprising the bead complex, can be provided. For example, the container may be a cosmetic container, a fish tank, a water tank, or a beverage container, and the bead complex may be stably coated on an inner wall of the cosmetic container, a fish tank, a water tank, or a beverage container to prevent the antibacterial and oxidation of the contents of the container. Prevention, sterilization and the like can be provided.

According to the embodiments of the present invention, zeolite nanoparticles or microparticles are coated with zeolite directly on the surface of the beads by putting naked beads such as alumina, silica, glass, plastics, etc., which are not coated directly into the synthetic gel. That is, the zeolite coated beads made by direct synthesis without zeolite seed crystals can be prepared, and the coated beads can be put in a liquid such as cosmetics to provide an antimicrobial effect.

Figure 1, in one embodiment of the present application, shows a schematic diagram of a bead composite and a manufacturing process comprising the molecular sieve crystal particles coated on the beads through a linking compound coated on the surface of the beads.

Figure 2 shows an electron micrograph of the spherical glass beads (Comparative Example) not coated with the zeolite crystal particles and the spherical glass bead composite (Example) coated with the zeolite crystal particles.

Figure 3, in one embodiment of the present application, shows an electron micrograph of the spherical glass bead composite coated with the zeolite crystal particles [scale bar: (A, C, D) 1 μm, scale bar: (B) 10 μm].

Figure 4, in one embodiment of the present application, shows an electron micrograph of the donut-type plastic bead composite coated with the zeolite crystal particles [scale bar: (A, B) 1 μm].

FIG. 5 is an electron micrograph of a bead composite coated with zeolite Y crystal particles directly on the surface of the beads through hydrothermal synthesis by putting silica beads into a zeolite Y synthetic gel without using zeolite seed particles. (Scale bar: 250 μm).

FIG. 6 shows an electron micrograph of a bead composite coated with zeolite Y crystal particles on the surface of the beads through hydrothermal synthesis by inserting silica beads coated with zeolite seed particles in a zeolite Y synthetic gel in accordance with an embodiment of the present disclosure. (Scale bar: 200 μm).

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a part is said to be "connected" with another part, this includes not only the "directly connected" but also the "electrically connected" between other elements in between. do.

Throughout this specification, when a member is located “on” another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated. As used throughout this specification, the terms “about”, “substantially”, and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are provided, and an understanding of the present application may occur. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term “step of” or “step of” does not mean “step for”.

Throughout this specification, the term "combination (s) thereof" included in the expression of a makushi form refers to one or more mixtures or combinations selected from the group consisting of components described in the expression of makushi form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, the description of “A and / or B” means “A or B, or A and B”.

Hereinafter, with reference to the accompanying drawings will be described embodiments and embodiments of the present application; However, the present disclosure may not be limited to these embodiments, examples, and drawings.

In one embodiment of the present application, the chemical bond may be to include a hydrogen bond, ionic bond, non-covalent bond, covalent bond or coordination bond, but is not limited thereto.

In one embodiment of the present application, the hydrogen bond may be formed directly between the surface of the bead and the molecular sieve crystal particles or formed through a hydrogen bond medium, but is not limited thereto.

In one embodiment of the present application, one or more linking compounds may be formed between the surface of the beads and the molecular sieve crystal particles, but is not limited thereto.

In one embodiment of the present application, the at least one linking compound is formed between the surface of the bead and the molecular sieve crystal particles are bonded to each other and then remove the linking compound by firing the surface of the beads and the molecular sieve crystal particles May be formed by direct chemical bonding, but is not limited thereto.

In one embodiment of the present application, the molecular sieve may include, but are not limited to, an ion exchanged or adsorbed metal or metal cation, or a coordination compound, an antioxidant or a preservative.

In one embodiment of the present application, the molecular sieve may include, but is not limited to, an ion exchanged or adsorbed metal or metal cation.

In one embodiment of the present application, the metal or metal cation may include Ag, Cu, Zn, Ti, Pt, Pd or Au, or a cation of the metal, but is not limited thereto.

In one embodiment of the present application, the bead complex may have a catalyst or photocatalyst properties in addition to the molecular sieve, and may further include a metal compound capable of supporting a metal, but is not limited thereto.

In one embodiment of the present application, the metal compound may include an oxide of one or two or more metals selected from Mg, Al, Au, Ag, Pd, Pt, Ti, Zn, and Si, for example For example, it may include ZnO, SiO ₂ or TiO ₂ , but is not limited thereto.

In one embodiment of the present application, the metal that can be supported on the metal compound may include Ag, Cu, Pt, or Pd, but is not limited thereto.

In one embodiment of the present application, the molecular sieve may include, but is not limited to, a material selected from the group consisting of:

(i) zeolite

(ii) zeolite, ZSM-5, silicalite-1, TS-1 or metallo-silicalite-1 with MFI structure

(iii) zeolite with MEL structure, ZSM-11, silicalite-2, TS-2 or metallo-silicalite-2

(iv) zeolite A, X, Y, L, beta, mordenite, ferrierite, ETS-4 or ETS-10

(v) mesoporous silica of any of MCM series, SBA series, MSU series or KIT series

(vi) organic-inorganic composite mesoporous structures or layered materials

(vii) organo zeolites, organometallic zeolites or coordination compounds zeolites in which metal ions and ligands are three-dimensionally bonded

(viii) complexes containing organic, inorganic, organic-inorganic mixed dyes, luminescent dyes or pigments within the pores of a porous material or between layers of a layered material, and

(ix) Metal Organic Framework (MOF) materials, Covalent Organic Framework (COF) materials, or complexes thereof.

In one embodiment of the present application, the bead may include one or more materials selected from the group consisting of an organic polymer, an inorganic polymer, an organic-inorganic hybrid polymer, plastic, metal, glass, and ceramic, but is not limited thereto. It is not.

In one embodiment of the invention, the beads may have a variety of forms and / or a variety of colors, for example, the beads are spherical, oval, or polyhedral (cuboid, cuboid, cylindrical, tetrahedral, octahedral, etc.) It may be, but is not limited thereto.

In one embodiment of the present application, the beads may have a size of about 1 mm or more, for example, may have a size of about 1 mm to about 10 cm, but is not limited thereto.

In one embodiment of the present disclosure, the beads may include, but are not limited to, a material selected from the group consisting of the following materials:

(i) Metals and oxides containing only one or more nonmetallic elements such as titanium dioxide, titanate, zinc oxide, etc. and having hydroxy groups on the surface: various metals and nonmetallic elements such as silicon, aluminum, titanium, tin and indium All substances in which these are the oxides which are contained individually or in 2 or more types, and have a hydroxyl group on the surface. For example, various conductive glasses such as quartz, mica, glass, ITO glass (glass on which indium tin oxide is deposited), or tin oxide (SnO ₂ ), silica, porous silica, alumina, porous alumina, titanium dioxide, porous titanium dioxide and Silicon wafers and the like;

(ii) metals which bind with thiol groups (-SH) or amine groups (-NH ₂ ) (including but not limited to gold, silver, copper, platinum, etc.);

(iii) polymers having various functional groups on the surface (including but not limited to polyvinyl chloride (PVC) and Merrifield peptide resin, etc.);

(vi) Semiconductor compounds of zinc selenide (ZnSe), gallium arsenide (GaAs) or indium phosphide (InP), or sulfides, selenium compounds or phosphides having semiconductor properties.

(v) porous microparticles such as zeolites, zeotypes, Metal Organic Framework (MOF) materials, Covalent Organic Framework (COF), or composites thereof, and

(vi) natural polymers having a hydroxyl group on the surface or being treated to have a hydroxyl group, synthetic polymers, or conductive polymers [including but not limited to natural polymers having hydroxyl groups on the surface such as cellulose, starch (amylose and amylopectin) and lignin, Synthetic polymers or conductive polymers].

In one embodiment of the invention, the beads and the molecular sieve crystals can be used as such without any pretreatment. As such, the beads and molecular sieve crystals without pretreatment are called bare beads and bare molecular sieve crystals, respectively. The beads and the molecular sieve crystals are chemically bonded to each other through functional groups in the pure beads and pure molecular sieve crystals themselves. As a non-limiting example, the bond between the pure beads and the pure molecular sieve crystals can be formed by hydrogen bonding.

In one embodiment of the present application, the hydrogen bonding between the beads and the molecular sieve crystals can be made using a suitable hydrogen bonding mediator to make the beads and / or molecular sieve crystals, whereby hydrogen bonding is further achieved. It can be formed stably with strong strength. For example, the surface of the bead and / or molecular sieve crystals may be coated (spin coated or dip coated) with a hydrogen bonding medium, and the molecular sieve crystals may be stably bonded with strong strength by applying pressure to the bead surface. Usable as the hydrogen bonding medium include, but are not limited to, polyethylene imine (PEI), 4-pyridinecarboxylic acid (PyC), and PyA [trans-3- (3-pyridyl) -acrylic acid].

In one embodiment of the present application, the beads and the molecular sieve are chemically bonded via the linking compound. In this case, a linking compound is bonded to the beads, or the molecular sieve, or the beads and the molecular sieve.

As used herein, the term "linking compound" refers to any compound having a functional group at the terminus that enables binding between the beads and the molecular sieve crystals.

In one embodiment of the present disclosure, the linking compound may include a compound derived from one or two or more organic compounds selected from the group consisting of the following compounds of Formulas 1 to 7, but is not limited thereto. .:

[Formula 1]

Z-L1-X

[Formula 2]

MR ' ₄

[Formula 3]

R ₃ Si-L1-Y

[Formula 4]

HS-L1-X

[Formula 5]

HS-L1-SiR ₃

[Formula 6]

HS-L1-Y

[Formula 7]

Z-L2 (+) L3 (−)-Y or Z-L3 (−) L2 (+)-Y;

Z in the formula is R ₃ Si or an isocyanate group (-NCO), wherein R represents a halogen group, an alkoxy group of C ₁ -C ₄ or an alkyl group of C ₁ -C ₄ and at least one of the three Rs is a halogen group or An alkoxy group,

L _{1 is a} hydrocarbon moiety such as a substituted or unsubstituted C ₁ -C ₁₇ alkyl, aralkyl or aryl group which may comprise one or more oxygen, nitrogen or sulfur atoms, X being a halogen, isocyanate (-NCO) group Is a tosyl group or an azide group, R 'is the same as R, at least two of the four R's are halogen or alkoxy groups, M is silicon, titanium or zirconium,

Y is a hydroxy group, thiol group, amine group, ammonium group, sulfone group and salts thereof, carboxylic acid and salts thereof, acid anhydride, epoxy group, aldehyde group, ester group, acrylic group, isocyanate group (-NCO), sugar residues, It is a coordination compound capable of double bond, triple bond, diene, diene, alkyl phosphine, alkyl acin and ligand exchange,

Y may be located in the middle as well as the terminal of the linking compound,

L 2 (+) represents a functional group having at least one positive charge (+) at the terminal, straight chain or side chain of a substituted or unsubstituted C 1 -C 17 hydrocarbon compound which may include one or more oxygen, nitrogen or sulfur atoms,

L 3 (-) means a functional group having at least one negative charge (-) at the terminal, straight or side chain of a substituted or unsubstituted C ₁ -C ₁₇ hydrocarbon compound which may contain one or more oxygen, nitrogen or sulfur atoms. do. The intermediate linking compounds include fullerenes (C ₆₀ , C ₇₀ ), carbon nanotubes, α, ω-dialdehydes, dicarboxylic acids, dicarboxylic acid anhydrides, amine-dendrimers, polyethyleneimines, α, ω-diamines, metal porphyrins and M ( Saline) is a compound selected from the group consisting of cobalt, nickel, chromium, manganese or iron, and saline is N, N'-bis (salicylidene) ethylenediamine.

In one embodiment of the present application, prior to binding the beads and the molecular sieve crystals, beads, molecular sieve crystals or beads and molecular sieve crystals are treated with the above-mentioned linking compound to have a functional group suitable for binding. In this way, (bead-linked compound) intermediates and / or (linked compound-molecule crystals) intermediates are prepared.

In one embodiment of the present disclosure, the (bead-linking compound) intermediate and / or the (linking compound-molecule crystal) intermediate may be carried out according to various compounds and processes known herein.

In one embodiment of the present application, the surface of the beads and molecular sieve crystals generally has a functional group such as a hydroxy group, or a functional group convertible to a hydroxyl group precursor or a hydroxyl group. Examples of hydroxy group precursors or functional groups convertible to hydroxy groups include acyloxy groups, methoxy groups or Si═O groups.

In one embodiment of the present application, the (bead-linked compound) intermediate and the (linked compound-molecule crystal) intermediate can form a direct chemical bond by themselves, but through an intermediate linking compound that mediates the bond between the intermediates. Indirect chemical bonding is possible. As used herein, the term "intermediate linking compound" means any compound having a functional group at the terminal that enables binding between two linking compounds between the (bead-linking compound) intermediate and the (linking compound-molecular crystal crystal) intermediate. . Preferably, the intermediate linking compound is fullerene (C ₆₀ , C ₇₀ ), carbon nanotube, α, ω-dialdehyde, amine, sulfonic acid, dicarboxylic acid, dicarboxylic anhydride, amine-dendrimer, polyethyleneimine , complexes represented by α, ω-diamine, metal porphyrin and M (salin), where M is cobalt, nickel, chromium, manganese or iron, and saline is N, N'-bis (salicylidene) ethylenediamine Selected from the group consisting of.

Y may be located in the middle as well as the terminal of the linking compound,

In one embodiment of the present application, the molecular sieve crystal particles may be bound to the surface of the beads, but is not limited thereto.

In another embodiment of the present application, the molecular sieve crystal particles may be bonded to the surface of the bead arranged in a predetermined direction, but is not limited thereto.

In one embodiment of the present application, the molecular sieve crystal particles or the additional particles comprising together with the molecular sieve crystal particles arranged to bind to the surface of the beads are antimicrobial, antioxidant, sterilization, adsorption of contaminants and / Or it may represent one or more functions of decomposition performance, deodorization, and humidity control, but is not limited thereto.

In one embodiment of the present application, the molecular sieve crystal may be a microcrystal, but is not limited thereto. The term “microcrystal” means a crystal having a size of about 0.1 μm to about 500 μm.

In one embodiment of the present application, the further comprising particles may have a nanometer size to micrometer size, but is not limited thereto.

In one embodiment of the present application, the molecular sieve crystals bound to the beads may have an orientation along a predetermined crystal axis with respect to the plane of the beads, but is not limited thereto. Such mono-orientation can maximize the application and utilization efficiency of the molecular sieve.

A second aspect of the present disclosure provides an article comprising the bead composite according to the first aspect of the present disclosure. All of the content described for the bead complex according to the first aspect of the present application also applies to the second aspect of the present application.

In one embodiment of the present application, the article may be a container containing a liquid, a semi-liquid, or a gel, but is not limited thereto. For example, the container may be a cosmetic container, a fish tank, a tank, or a beverage container, but is not limited thereto.

In one embodiment of the present application, the bead complex may be included in the contents of the container or coated on the inner wall of the container, but is not limited thereto.

In one embodiment of the present application, the molecular sieve crystal particles provide a bead complex stably coated on the surface of the beads having a variety of shapes, different colors, it can be provided a variety of articles using the bead complex.

In one embodiment of the present application, the bead complex is stably coated on the inner wall of the cosmetic container, fish tank, water tank, or beverage (for example, a variety of alcohol, such as water, rice wine, etc.) to the antibacterial, oxidation of the contents of the container Prevention, sterilization and the like can be provided.

In one embodiment of the present application, the composite coated with Ag ⁺ -ion exchanged zeolite Y crystal particles exhibits remarkably good antibacterial activity against a wide range of microorganisms such as Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Candida albicans, Aspergillus flavus, and the like. These results indicate that the glass bead composite and the plastic bead composite coated with zeolite crystal particles can be applied to antimicrobial beads, deodorants, adsorbents, sanitary materials, gas separation membranes, or ion exchangers. For example, each of the glass bead complex and the plastic bead complex as described above shows remarkably excellent antibacterial activity against a wide range of microorganisms such as Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Candida albicans, Aspergillus flavus, and the like.

The content described with respect to the first and second aspects of the present application also applies to the third aspect of the present application.

In one embodiment of the present application, the manufacturing method may further include coating a surface of each or both of the beads and the molecular sieve crystal particles with a hydrogen bonding medium before coating the molecular sieve crystal particles, It is not limited to this.

In one embodiment of the present application, the manufacturing method may further include removing the hydrogen bond medium by coating the molecular sieve crystal particles on the surface of the beads after coating with the hydrogen bond medium and then calcining. However, the present invention is not limited thereto.

In one embodiment of the present disclosure, the manufacturing method may further include bonding one or more connecting compounds to the surface of each or both of the beads and the molecular sieve crystal particles before coating the molecular sieve crystal particles. However, it is not limited thereto.

In one embodiment of the present application, the manufacturing method may further include removing the linking compound by bonding the linking compound and then coating the molecular sieve crystal particles on the surface of the bead and then firing it, It is not limited.

In one embodiment of the present invention, the coating of the molecular sieve crystal particles on the surface of the beads, the hydrogel reaction by immersing the beads in a synthetic gel solution for forming the molecular sieve crystal particles to directly the surface of the beads Molecular sieve crystal particles may be formed and coated, but is not limited thereto. For example, a shell of the molecular sieve crystal particles may be directly formed on the surface of the beads by immersing the beads in a synthetic gel solution for forming the molecular sieve crystal particles. By this manufacturing method, the zeolite crystal grains can be stably coated directly on the naked surface of the beads without pre-coating zeolite seed crystals on the surface of the beads, and the coating process can be significantly simplified. .

According to one embodiment of the present application, zeolite nanoparticles or microparticles are coated with zeolite directly on the surface of the bead by directly putting naked beads (naked bead), such as alumina, silica, glass, plastics, etc., which are not coated in a synthetic gel That is, the zeolite coated beads made by direct synthesis without zeolite seed crystals can be prepared, and the coated beads can be put in a liquid such as cosmetics to provide an antimicrobial effect.

In one embodiment of the present application, the linking compound and the coating of the molecular sieve crystal particles are each independently rubbing coating, spray coating, dip coating, ultrasonic using-coating, copper plate coating, or impregnated coating method It may be performed, but is not limited thereto.

For example, the coating of the molecular sieve crystal particles may include coating the molecular sieve crystal particles by rubbing the surface of the beads coated with the linking compound, or the beads coated with the linking compound By coating the molecular sieve crystal particles on the surface of the beads by adding the molecular sieve crystal particles to the beads, or by placing the beads coated with the linking compound into a solution containing the molecular sieve crystal particles and then performing ultrasonic treatment. It may be carried out by a process of coating the molecular sieve crystal particles on the bead surface, but is not limited thereto.

In one embodiment of the present application, the coating of the molecular sieve crystal grains by rubbing adds pressure in a manner against pressing or rubbing the molecular sieve crystal grains onto the surface of the beads. Pressing and / or forced surface migration of molecular sieve crystal grains generated during the scrubbing process during the scrubbing process may cause molecular sieve crystals to form on the beads at a high density. The two most important factors that lead to incorporation.

In one embodiment of the present application, the rubbing is associated with a chemical bond, in particular an ionic bond or a hydrogen bond, between the beads and the linking compound, the molecular sieve particles and the linking compound, the linking compound and the linking compound or the linking compound and the intermediate linking compound. Increasing the reaction activity of molecules (particularly functional groups) allows them to bond in a short time.

In one embodiment of the present application, in order to prepare the bead-molecular sieve particle complex, the method of applying pressure to the molecular sieve crystal grains, for example, pressure to the molecular sieve crystal grains using only the hands (bare hands) Can be applied by hand with a scrubbing tool, or pressure can be applied to the molecular sieve crystals using a scrubbing mechanism.

In one embodiment of the present disclosure, molecular sieve crystals of about 3 μm or more can also be bound onto the beads with high density (density) and high adhesion rates.

In one embodiment of the present application, the molecular sieve crystals form a chemical bond directly or indirectly to the bead surface. The chemical bonds include hydrogen bonds, non-covalent bonds, ionic bonds, covalent bonds and coordination bonds.

In one embodiment of the present application, the chemical bond may be an ionic bond or a hydrogen bond, but is not limited thereto. In another embodiment of the present disclosure, when the linking compound mediates a bond between the surface of the bead and the molecular sieve crystal particles, it may be an ionic bond. For example, among the binding patterns according to the present invention described above, the bead complex formed by the hydrogen bond may be (i) bead-molecular sieve complex or (ii) bead-hydrogen bond mediator-molecular sieve complex. The bead complex formed by the ionic bond may be (i) bead-linked compound-molecular sieve complex (ii) bead-linked compound-linked compound-molecular sieve complex, or (iii) bead-linked compound-intermediate linking compound-linking Compound-molecular complex.

In one embodiment of the present application, when spraying the composition for the particle-spray coating to the beads, the molecular sieve crystals bound to the beads are substantially parasitic crystal (parasitic crystal). Parasitic crystals growing inside the mother crystal of the molecular sieve have a problem that greatly degrades the functionality of the molecular sieve. However, in one embodiment of the present application, by simply spraying the composition for the particle-spray coating to the beads, by coating the beads with the molecular sieve crystal particles on the surface of the beads without the formation of parasitic crystals, for example For example, the molecular sieve monolayer film can be formed on the beads.

In one embodiment of the present application, the first molecular sieve crystal monolayer film is first formed on the beads according to the above-listed method, and the second molecular sieve crystal capable of binding to the first molecular sieve monolayer film binds the bilayer to the beads. Films can be stacked, and this process can be repeated to produce a multilayer film. The second molecular sieve crystal may be of the same kind or a different kind from the first molecular sieve crystal forming the monolayer film. The lamination pattern is not limited to a specific method, for example, (bead-linked compound-first molecular sieve crystal)-(linked compound-second molecular sieve crystal), (bead-linked compound)-(linked compound-first) Molecular sieve crystal-linked compound)-(linked compound-second molecular sieve crystal) and the like.

In one embodiment of the present application, according to the methods listed above, after the first generation of the molecular sieve monolayer film (monolayer) in the beads and firing at high temperature to remove the linking compound, the beads and molecular sieve is silicon-oxygen-silicone, etc. It is bound by direct chemical bonding. By repeating this process, a multilayer can be obtained in which beads and molecular sieves are directly bonded. On the other hand, it is clear that the manufacturing method according to the embodiments of the present application can also be used in the production of a film of molecular sieve crystals according to the conventional techniques in the art in view of the technical level in the art.

Hereinafter, the present invention will be described in more detail with reference to examples of the present application, but the following examples are merely illustrated to aid the understanding of the present application, and the content of the present application is not limited to the following examples.

[실시예]EXAMPLE

<실시예 1><Example 1>

A powder comprising Ag ⁺ -ion exchanged zeolite Y crystal particles and a linking compound or a composition comprising the powder is coated on the surfaces of spherical glass beads (size: 3 mm) and donut plastic beads, respectively, to the surface of the beads. A bead composite was prepared, comprising zeolite Y crystal particles coated on the beads through the coated linking compound. Electron micrographs of each of the composites are shown in FIGS. 2 to 4, respectively.

FIG. 2 shows electron micrographs of spherical glass beads (Comparative Example) not coated with the zeolite Y crystal particles and spherical glass bead composites (Example) coated with the zeolite Y crystal particles.

Figure 3 shows an electron micrograph of the spherical glass bead composite (Example) coated with the zeolite Y crystal particles. Referring to FIG. 3, it can be seen that the zeolite Y crystal particles are uniformly and densely coated on the surface of the glass beads.

Figure 4 shows an electron micrograph of the donut-like plastic bead composite (Example) coated with the zeolite Y crystal particles. Referring to FIG. 4, it can be seen that the zeolite Y crystal particles are uniformly and densely coated on the surface of the plastic beads.

<실시예 2><Example 2>

After coating the zeolite Y seed crystals on the surface of the silica beads by impregnation method, the beads were added to the zeolite Y synthetic gel and hydrothermally synthesized at 100 ° C. for about 3 hours to coat the seed beads with silica zeolite on the surface of the bead composite. Was formed. An electron micrograph of the composite is shown in FIG. 5.

On the other hand, without coating the zeolite Y seed crystals on the surface of the silica beads, the silica beads were originally added to the zeolite Y synthetic gel and hydrothermally synthesized at 100 ° C. for about 3 hours to form zeolite Y crystal particles on the naked surface of the silica beads. The coating formed a bead composite. An electron micrograph of the composite is shown in FIG. 6. Referring to FIG. 6, it can be seen that the zeolite Y crystal grains can be stably and uniformly coated on the naked surface of the silica beads even when the zeolite Y seed crystals are not previously coated.

<실험예>Experimental Example

In order to test the antimicrobial effect of the bead composite coated with Ag ⁺ -ion exchanged zeolite Y crystal particles synthesized in Example 1, the antiseptic test was performed as follows, and the results are shown in Tables 1 and 2 below. It was.

As a result of antiseptic test, the antiseptic effect of the bead complex was remarkably excellent.

For reference, in the present experimental example, the bacterial preservation acceptance criteria was 3 log or more on the 7th day, and compared with the beads coated with the zeolite Y crystal particles, the synthesized Ag ⁺ -ion exchanged zeolite Y crystal particles were coated. The bead complex showed a killing effect of 3 log or more after 1 day, and no bacteria were detected after 7 days.

For the interpretation of the results, two methods were used: the measured bacterial counts and the log kill rate.

Test strains: E. coli, S. aureus (gram negative, one positive each)

-Test method: Inoculated with the zeolite beads at 0.5% concentration in the skeletal formulation with almost no preservative force, and inoculated with the bacteria.

검출균수(cfu)Detection of bacteria (cfu)

	균주Strain	Day 1Day 1	Day 2Day 2	Day 7Day 7
제올라이트 코팅되지 않은 비드Zeolite uncoated beads	E. coliE. coli	TNTCTNTC	TNTCTNTC	TNTCTNTC
제올라이트 코팅되지 않은 비드Zeolite uncoated beads	S. aureusS. aureus	TNTCTNTC	TNTCTNTC	TNTCTNTC
Ag(1%) 교환된-zeolite 비드Ag (1%) exchanged-zeolite beads	E. coliE. coli	7878	4848	<1<1
Ag(1%) 교환된-zeolite 비드Ag (1%) exchanged-zeolite beads	S. aureusS. aureus	3030	<1<1	<1<1
Ag(2.5%) 교환된 -zeolite 비드Ag (2.5%) exchanged -zeolite beads	E. coliE. coli	1414	<1<1	<1<1
	S. aureusS. aureus	<1<1	<1<1	<1<1

log 사멸률log mortality

	균주Strain	Day 1Day 1	Day 2Day 2	Day 7Day 7
Ag(1%) 교환된-zeolite 비드Ag (1%) exchanged-zeolite beads	E. coliE. coli	3.113.11	3.323.32	>5> 5
Ag(1%) 교환된-zeolite 비드Ag (1%) exchanged-zeolite beads	S. aureusS. aureus	3.523.52	>5> 5	>5> 5
Ag(2.5%) 교환된 -zeolite 비드Ag (2.5%) exchanged -zeolite beads	E. coliE. coli	3.853.85	>5> 5	>5> 5
	S. aureusS. aureus	>5> 5	>5> 5	>5> 5

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application.

Claims

A bead composite comprising molecular sieve crystal grains coated through chemical bonding to the surface of a bead.
The method of claim 1,

The chemical bond is a bead complex, including a hydrogen bond, ionic bond, non-covalent bond, covalent bond or coordination bond.
The method of claim 1,

The molecular sieve crystal particles bound to the beads are coated with a single orientation with respect to the plane of the beads.
The method of claim 2,

Wherein the hydrogen bond is formed directly between the surface of the bead and the molecular sieve crystal particles or is formed through a hydrogen bond medium.
The method of claim 1,

Will be formed by combining at least one linking compound between the surface of the beads and the molecular sieve crystal particles.
The method of claim 5,

The one or more linking compounds are formed by bonding between the surface of the bead and the molecular sieve crystal particles, and then the surface of the bead and the molecular sieve crystal particles are directly chemically bonded by removing the linking compound by firing. Will bead complex.
The method of claim 1,

The molecular sieve comprises a metal or metal cation that is ion exchanged or adsorbed, or comprises a coordination compound, an antioxidant or a preservative.
The method of claim 7, wherein

The metal or metal cation comprises a metal having an antioxidant, antimicrobial or catalytic or photocatalytic properties or cations of the metal, bead composite.
The method of claim 7, wherein

The metal or metal cation is Ag, Cu, Zn, Ti, Pt, Pd or Au, or bead composite containing the cation of the metal.
The method of claim 1,

In addition to the molecular sieve crystal particles, having a catalyst or photocatalyst properties, and further comprising a metal compound particles that can be supported on the metal, bead composite.
The method of claim 10,

The metal compound is a bead composite comprising an oxide of one or two or more metals selected from Mg, Al, Au, Ag, Pd, Pt, Ti, Zn, and Si.
The method of claim 10,

The metal compound is ZnO, SiO 2 or TiO 2 , bead composite.
The method of claim 10,

Metal that can be supported on the metal compound is Ag, Cu, Pt, or Pd, will bead composite.
The method of claim 1,

The molecular sieve comprises a material selected from the group consisting of, bead complex:

(i) zeolite

(ii) zeolite, ZSM-5, silicalite-1, TS-1 or metallo-silicalite-1 with MFI structure

(iii) zeolite with MEL structure, ZSM-11, silicalite-2, TS-2 or metallo-silicalite-2

(iv) zeolite A, X, Y, L, beta, mordenite, ferrierite, ETS-4 or ETS-10

(v) mesoporous silica of any of MCM series, SBA series, MSU series or KIT series

(vi) organic-inorganic composite mesoporous structures or layered materials

(vii) organic zeolites, organometallic zeolites or coordination compound zeolites in which metal ions and ligands are three-dimensionally bonded

(viii) complexes containing organic, inorganic, organic-inorganic mixed dyes, luminescent dyes or pigments within the pores of a porous material or between layers of a layered material, and

(ix) Metal Organic Framework (MOF) materials, Covalent Organic Framework (COF), or complexes thereof.
The method of claim 1,

The bead is a composite of beads comprising one or more materials selected from the group consisting of organic polymers, inorganic polymers, organic-inorganic hybrid polymers, metals, glass, plastics, and ceramics.
The method of claim 1,

The bead complex, wherein the bead comprises one or more materials selected from the group consisting of:

(i) A substance having a hydroxyl group on its surface as an oxide containing only one or more metals and nonmetallic elements such as titanium dioxide, titanate and zinc oxide.

(ii) metals bonded with thiol groups (-SH) or amine groups (-NH 2 )

(iii) polymers having functional groups on the surface

(vi) Semiconductor compounds of zinc selenide (ZnSe), gallium arsenide (GaAs) or indium phosphide (InP), or sulfides, selenium compounds or phosphides having semiconductor characteristics

(v) porous microparticles such as zeolites, zeotypes, metal organic framework (MOF) materials, covalent organic framework (COF), composites thereof, and

(vi) Natural polymers, synthetic polymers, or conductive polymers having a hydroxy group on the surface or being treatable to have a hydroxy group.
The method of claim 1,

The linking compound is a bead complex comprising a compound derived from one or two or more organic compounds selected from the group consisting of the following compounds of Formulas 1-7:

[Formula 1]

Z-L1-X

[Formula 2]

MR ' 4

[Formula 3]

R 3 Si-L1-Y

[Formula 4]

HS-L1-X

[Formula 5]

HS-L1-SiR 3

[Formula 6]

HS-L1-Y

[Formula 7]

Z-L2 (+) L3 (−)-Y or Z-L3 (−) L2 (+)-Y;

In the above formula,

Z is R 3 Si or an isocyanate group (-NCO), wherein R represents a halogen group, an alkoxy group of C 1 -C 4 or an alkyl group of C 1 -C 4 and at least one of the three Rs is a halogen group or an alkoxy group ,

L 1 is a hydrocarbon moiety such as a substituted or unsubstituted C 1 -C 17 alkyl, aralkyl or aryl group which may comprise one or more oxygen, nitrogen or sulfur atoms, X being a halogen, isocyanate (-NCO) group Is a tosyl group or an azide group, R 'is the same as R, at least two of the four R's are halogen or alkoxy groups, M is silicon, titanium or zirconium,

Y is a hydroxy group, thiol group, amine group, ammonium group, sulfone group and salts thereof, carboxylic acid and salts thereof, acid anhydride, epoxy group, aldehyde group, ester group, acrylic group, isocyanate group (-NCO), sugar residues, It is a coordination compound capable of double bond, triple bond, diene, diene, alkyl phosphine, alkyl acin and ligand exchange, Y may be located at the end of the linking compound as well as in the middle, and L2 ( +) Represents a functional group having at least one positive charge (+) at the terminal, straight or side chain of a substituted or unsubstituted C1-C17 hydrocarbon compound which may include one or more oxygen, nitrogen or sulfur atoms, and L3 (- ) Means a functional group having at least one negative charge (-) at the terminal, straight or side chain of a substituted or unsubstituted C 1 -C 17 hydrocarbon compound which may include one or more oxygen, nitrogen or sulfur atoms.
The method according to any one of claims 1 to 17,

Wherein the molecular sieve crystal particles or the metal compound particles bound to the surface of the beads exhibit at least one function of antioxidant, water purification, antimicrobial properties, adsorption and / or decomposition performance of pollutants, deodorization, and humidity control. Bead complex.
The method of claim 1,

The bead complex, wherein the bead has a spherical, oval, cylindrical, or polyhedral form.
20. An article comprising the bead composite according to any one of claims 1 to 19.
The method of claim 20,

The article may be liquid, semi-liquid, gel, gas Or a container containing a solid.
The method of claim 21,

Wherein the container is a cosmetic container, a fish tank, a fish tank, a fish farm, or a beverage container.
The method of claim 21,

Wherein the container is a container through which air is passed for air purification.
20. The method of claim 1, further comprising chemically bonding the molecular sieve crystal particles to the surface of the beads by coating molecular sieve crystal particles on the surface of the beads.
The method of claim 24,

The coating of the molecular sieve crystal particles according to any one of claims 1 to 19, wherein the coating of the molecular sieve crystal particles is carried out by a rubbing coating, spray coating, dip coating, ultrasonic wave-coating, copper coating, or impregnation coating method. Process for the preparation of the complex according to claim.
The method of claim 24,

Prior to coating the molecular sieve crystal particles, further comprising coating a surface of each or both of the beads and the molecular sieve crystal particles with a hydrogen bonding medium,

20. A method for producing the bead composite according to any one of claims 1 to 19.
The method of claim 26,

After the coating with the hydrogen bond medium, the molecular sieve crystal particles further comprises coating on the surface of the beads and then firing to remove the hydrogen bond medium,

20. A method for producing the bead composite according to any one of claims 1 to 19.
The method of claim 24,

Prior to coating the molecular sieve crystal particles, further comprising coupling one or more linking compounds to the surface of each or both of the beads and the molecular sieve crystal particles,

20. A method for producing the bead composite according to any one of claims 1 to 19.
The method of claim 28,

Further comprising removing the linking compound by binding the linking compound and then coating the molecular sieve crystal particles on the surface of the bead, followed by calcination.

20. A method for producing the bead composite according to any one of claims 1 to 19.
The method of claim 24,

The coating of the molecular sieve crystal particles on the surface of the beads may include hydrothermal reaction by dipping the beads in a synthetic gel solution for forming the molecular sieve crystal particles to form the molecular sieve crystal particles directly on the surface of the beads. 20. A method for producing the bead composite according to any one of claims 1 to 19, which comprises.