KR102125317B1 - Apparatus for coating fine particles by spraying in solution, and method for preparing substrate-fine particle coating composite by using the same - Google Patents

Abstract

Provided is a method for manufacturing a substrate-fine particle membrane composite using liquid spray such as underwater spray, and a liquid spray type fine particle coating device used therein.

Description

Manufacturing method of microparticle coating device using liquid spray and substrate-microparticle film composite using the same{APPARATUS FOR COATING FINE PARTICLES BY SPRAYING IN SOLUTION, AND METHOD FOR PREPARING SUBSTRATE-FINE PARTICLE COATING COMPOSITE BY USING THE SAME}

The present application relates to a microparticle coating device using submerged spraying, such as underwater spraying, and a method for producing a substrate-microparticle membrane composite using the coating device.

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

The simplest method was to immerse the substrate in a turbid solution made of zeolite crystals to attach the zeolite particles by physical attraction between the surface of the zeolite and the surface of the substrate [L. C. Boudreau, J. A. Kuck, M. Tsapatsis, J. Membr. Sci. 1999, 152, 41-59]. Since this method is a method of controlling the degree of dispersion of the zeolite by controlling the rate at which the zeolite is taken out of the turbid solution, it is difficult to form a uniform monolayer film of the zeolite particles, and since the zeolite is simply physically adsorbed on the substrate, the particles are removed from the substrate. There was a tendency to escape easily.

As another conventional method, (1) the substrate and the linking compound (intermediate 1) are covalently bound, and the molecular sieve particle and the linking compound (intermediate 2) are covalently linked, and then the intermediate 1 and the intermediate compound 1 are used using functional groups at the ends of the linking compound Method for forming a substrate-molecular sieve membrane complex by covalently, ionically or coordinating intermediate 2, (2) covalently binding one end of a linking compound with a substrate or molecular sieve particle, and the other end of the linking compound is a substrate or Method of forming a substrate-molecular sieve membrane complex by directly binding to a molecular sieve, (3) Inserting an intermediate linking compound between intermediate 1 and intermediate 2 to control the length between the substrate and the molecular sieve particle while controlling the substrate-molecular sieve membrane complex A method of forming, and (4) a method of repeatedly forming (1) to (3) to form a multi-layered molecular sieve membrane on a substrate, etc., which is disclosed, which is a substrate-molecular sieve membrane composite can be applied as an advanced new material. Although it has made a significant contribution, energy efficiency and adhesion speed are low because simple reflux is used in the bonding between the substrate and the linking compound, molecular sieve particles and linking compound, linking compound and linking compound, and linking compound and intermediate linking compound. , The density between the attached zeolite particles was poor, and the bonding strength between the attached zeolite and the substrate was weak. In addition, mass production was difficult due to the limitation of simple reflux.

In addition, since the proposed methods attach zeolite to a substrate (fabric, etc.) by a chemical method, a separate process for this takes a lot of processing cost depending on the design, and it is necessary to perform a separate process from the substrate processing process. And there was a problem that the process efficiency is reduced according to the process time.

Republic of Korea Patent Registration Publication No. 10-0395902

The present application relates to a microparticle coating device using submerged spraying, such as underwater spraying, and a method for producing a substrate-microparticle membrane composite using the coating device.

However, the problems to be solved by the present application are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present application provides an apparatus for spraying microparticles in a liquid, comprising:

A first transfer unit for transferring the substrate;

A coating unit coating the substrate continuously transferred from the first transfer unit by microparticles; And

A second transfer unit for recovering the coated substrate from the coating unit

Including, in-spray injection microparticle coating apparatus,

The coating unit,

A container containing a microparticle-containing solution;

A spray nozzle for coating the microparticles on the substrate by spraying the microparticle-containing solution toward the substrate in a container containing the microparticle-containing solution;

A reflector and a support to prevent the substrate from being pushed or deformed from the sprayed solution; And

Removal roller for removing excess microparticles or the microparticle-containing solution sprayed on the substrate

It includes.

The second aspect of the present application is to form a matrix-microparticle film complex by coating the microparticles on the surface of the substrate by applying a liquid spray in the solution while passing the substrate through a container containing the microparticle-containing solution. It provides a method for producing a substrate-fine particle membrane composite using a spray, including.

According to the embodiments of the present application, a submerged injection type microparticle coating apparatus for manufacturing a substrate-fine particle membrane complex using submerged injection such as underwater spraying and a method of manufacturing a substrate-fine particle membrane composite using submerged injection using the apparatus Is provided.

According to the embodiments of the present application, by using a liquid injection such as underwater spray, by applying translational kinetic energy and vibration energy, instead of a substrate and a connecting compound, simple reflux, fine particles and connecting compounds, connecting compounds and connecting compounds or connecting compounds By inducing covalent, ionic, coordination or hydrogen bonds between intermediate linking compounds, it is possible not only to bind the substrate and microparticles in various ways, but also to save time and has a remarkably high adhesion speed, adhesion strength, adhesion accuracy and density. In the case where the substrate to which the linking compound is bound and the substrate to which the linking compound is mixed are, it is possible to selectively attach the fine particles evenly to both the substrate to which the linking compound is bound, which can be improved to enable mass production of the substrate-microparticle membrane complex. have.

According to embodiments of the present application, a method for manufacturing a submerged microparticle coating device such as underwater spraying and a substrate-fine particle membrane composite using submerged spraying using the device includes: fiber, wallpaper, closet product, blinder, curtain, plastic Or, a substrate or a transport portion for transporting a substrate such as a polymer, a plurality of spray nozzles for spraying microparticles toward the substrate, and a reflective plate and a support for preventing the substrate from being pushed or deformed from the sprayed solution, an excessive aqueous solution attached to the fiber It includes a device for removing the and includes a container containing a solution in which the fine particles are dispersed. Thereby, the microparticles can be strongly, uniformly and rapidly attached to the substrate by applying the translational kinetic energy and vibration energy by evenly spraying the solution in which the microparticles are dispersed on the substrate transferred at a constant speed.

According to the embodiments of the present application, formaldehyde showing sick house syndrome by uniformly and strongly coating fine particles such as zeola art on one or both sides of a substrate such as a fiber, wallpaper, closet product, blinder, curtain, plastic, or polymer, etc. , Benzene, toluene, volatile organic solvents, and chemical mass destruction gases during war, mustard gas, phosgene, phosgen, sarin, chlorine gas, and radioactive gas, which can be used to adsorb radioactive iodine .

Figure 1a, in one embodiment of the present application, is a block diagram of a microparticle coating apparatus in a liquid injection type.
1B is, in one embodiment of the present application, a block diagram of an apparatus for coating microparticles in a liquid injection type.
1C is, in one embodiment of the present application, a block diagram of an apparatus for coating microparticles in a liquid injection type.
Figure 2a, in one embodiment of the present application, is a schematic diagram of a liquid injection type microparticle coating apparatus.
Figure 2b, in one embodiment of the present application, is a schematic diagram of a liquid injection type microparticle coating apparatus.
Figure 3a, in one embodiment of the present application, is a block diagram of an apparatus for spraying microparticles in liquid.
Figure 3b, in one embodiment of the present application, is a block diagram of an apparatus for spraying microparticles in liquid.
Figure 4, in one embodiment of the present application, shows an SEM image of a blinder with zeolite attached using an underwater spray method, and a SEM image of a blinder without zeolite as a comparative example.
5 shows, in one embodiment of the present application, an SEM image of a blinder with zeolite attached using an underwater spray method.
Figure 6, in one embodiment of the present application, shows an SEM image of a blinder with zeolite attached using an underwater spray method.
7 shows, in one embodiment of the present application, a SEM image after 20 seconds of washing a blinder to which a zeolite is attached with an ultrasonic cleaner.
8 shows, in one embodiment of the present application, an SEM image of a wallpaper with zeolite attached using an underwater spray method, and a SEM image of a wallpaper without zeolite attached as a comparative example.
9 shows, in one embodiment of the present application, an SEM image of a wallpaper with zeolite attached using an underwater spray method.
10 shows, in one embodiment of the present application, SEM images after 20 seconds of washing the wallpaper with zeolite attached with an ultrasonic cleaner.
11 shows, in one embodiment of the present application, SEM images after 20 seconds of washing the wallpaper with zeolite attached with an ultrasonic cleaner.

Hereinafter, embodiments of the present application will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present application pertains may easily practice. However, the present application may be implemented in various different forms and is not limited to the embodiments described herein. In addition, in order to clearly describe the present application in the drawings, parts irrelevant to the description are omitted, and like reference numerals are assigned to similar parts throughout the specification.

Throughout this specification, when one member is positioned “on” another member, this includes not only the case where one member abuts another member, but also the case where another member exists between the two members.

Throughout the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated. The terms “about”, “substantially”, etc., used to the extent of the present specification are used in or near the numerical values when manufacturing and substance tolerances unique to the stated meanings are presented, and To aid, accurate or absolute figures are used to prevent unscrupulous use of the disclosed disclosure by unscrupulous infringers. The terms “~(steps)” or “steps of” as used in the present specification do not mean “steps for”.

Throughout the present specification, the term “combination(s)” included in the expression of the marki form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the marki 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, embodiments and examples of the present application will be described in detail with reference to the accompanying drawings. However, the present application may not be limited to these embodiments and examples and drawings.

A first aspect of the present application provides an apparatus for spraying microparticles in a liquid, comprising:

A first transfer unit for transferring the substrate;

A coating unit coating the substrate continuously transferred from the first transfer unit by microparticles; And

A second transfer unit for recovering the coated substrate from the coating unit

Including, in-spray injection microparticle coating apparatus,

The coating unit,

A container containing a microparticle-containing solution;

A spray nozzle for coating the microparticles on the substrate by spraying the microparticle-containing solution toward the substrate in a container containing the microparticle-containing solution;

A reflector and a support to prevent the substrate from being pushed or deformed from the sprayed solution; And

Removal roller for removing excess microparticles or the microparticle-containing solution sprayed on the substrate

It includes.

In one embodiment of the present application, the spray nozzle is located inside the container containing the microparticle-containing solution.

In one embodiment of the present application, the spray nozzle may be located on both side wall portions and/or underside portions of the inner portion of the container containing the microparticle-containing solution.

Referring to Figure 1a, in one embodiment of the present application, the liquid injection type microparticle coating apparatus, a first transfer unit 10 for transferring a substrate; A coating unit 100 coating the substrate continuously transferred from the first transfer unit by microparticles; And a second transfer part 10' for recovering the coated substrate from the coating part, but may not be limited thereto.

Referring to Figure 1b, in one embodiment of the present application, the liquid injection-type microparticle coating apparatus, to further include a temperature control unit A (110) for adjusting the temperature of the microparticle-containing solution in the coating unit It may, but may not be limited to this. For example, the temperature of the microparticle-containing solution may be controlled to about 0° C. to about 100° C. by the temperature control unit A 110, but may not be limited thereto.

Referring to FIG. 1C, in one embodiment of the present application, the solution used to supply the solution to a container containing the microparticle-containing solution in the coating part 100 and used from the container containing the microparticle-containing solution It may be to further include an external storage unit 130 for circulating the solution to recover, but may not be limited thereto.

Referring to Figure 1c, in one embodiment of the present application, the external storage unit 130 may be provided with a temperature control unit B 120, but may not be limited thereto. For example, the temperature of the external storage unit may be adjusted to about 0°C to about 100°C by the temperature control unit B 120, but may not be limited thereto.

Referring to Figure 1c, in another embodiment of the present application, the temperature of the external storage unit 130 to the temperature control unit A 110 for controlling the temperature of the microparticle-containing solution in the coating unit 100 It may be controlled by, but may not be limited to this.

Referring to Figure 2a and 2b, the liquid injection type microparticle coating apparatus according to an embodiment of the present application, the first transfer unit 10 for transferring the substrate (S); As a container (21) containing a microparticle-containing solution (20), the microparticles contain functional groups that can adhere to the surface of the substrate; A spray nozzle (30) for spraying the microparticle-containing solution in water toward the substrate in a container containing the microparticle-containing solution; A reflector and a support 40 to prevent the substrate from being pushed or deformed from the sprayed solution; A removal roller (50) for removing excess microparticle-containing solution adhering to the substrate; And it may include a second transfer unit (10') for recovering the substrate that has passed through the removal roller, but is not limited thereto. One or more of the spray nozzle 30 may be located in the inner wall of the container 21 containing the microparticle-containing solution 20 and the solution (Fig. 1A), or one or more of the spray nozzle 30 The microparticle-containing solution 20 may be located on the inner wall of the container 21 (FIG. 1B), but the application is not limited thereto.

In one embodiment of the present application, the spray nozzle may be disposed on both sides of the substrate, but may not be limited thereto.

In one embodiment of the present application, the spray nozzle may be disposed in two or more rows along the transport direction of the substrate, but may not be limited thereto.

In one embodiment of the present application, the microparticles included in each of the containers containing the microparticle-containing solution contained in each of the coating units and connected to two or more coating units are the same or different from each other, or the coating unit Two or more containers containing the microparticle-containing solution are provided therein, and the microparticles contained in each of the containers are the same or different from each other.

It may, but may not be limited to this. For example, the solvent contained in the microparticle-containing solution may be appropriately selected in consideration of the physicochemical properties of the microparticles and the substrate used such as water or alcohols or organic solvents.

In one embodiment of the present application, the spray nozzle may be to spray the fine particles in the range of about 0.01 g to about 1 g per 1 m ² of the substrate, but may not be limited thereto.

In one embodiment of the present application, the microparticles may contain functional groups that can be attached to the surface of the substrate, but may not be limited thereto.

In one embodiment of the present application, the substrate may include fibers, wallpaper, closet products, blinders, curtains, plastics, or polymers, but may not be limited thereto.

Referring to Figures 3a and 3b, in one embodiment of the present application, the liquid injection type microparticle coating apparatus, the drying unit 200 disposed between the coating unit 100 and the second transfer unit (10') It may be to further include, but may not be limited thereto.

In one embodiment of the present application, two or more drying units may be disposed along the transport direction of the substrate, but may not be limited thereto.

In one embodiment of the present application, the submerged injection type microparticle coating device may further include a chamber surrounding the injection nozzle, the removal roller, and the drying unit, but may not be limited thereto.

Referring to Figure 3a, in one embodiment of the present application, the liquid injection type microparticle coating apparatus, the foaming unit 300 and / or disposed between the drying unit 200 and the second transfer unit (10') The embossing unit 400 may further include, but may not be limited to.

Referring to Figure 3b, in one embodiment of the present application, the liquid injection type microparticle coating apparatus, further comprising a foaming portion 300 disposed between the first transfer portion 10 and the coating portion 100 It may be, but may not be limited to this.

In one embodiment of the present application, the liquid-injection type microparticle coating apparatus removes impurities remaining on the surface of the substrate after additional processes such as foaming, embossing, or the like after drying the substrate on which the microparticle coating has been completed. To this end, a plasma processing unit for plasma processing may be additionally provided at the front end of the second transfer unit, but may not be limited thereto. The plasma processing unit is equipped with a device such as oxygen plasma or Ar plasma to dry the substrate on which the microparticle coating has been completed, or by performing plasma treatment on the surface of the substrate after additional drying such as foaming, embossing, etc. Residual impurities and the like can be removed.

By using the liquid injection type microparticle attachment device, the microparticles are applied to fibers, wallpaper, closet products, blinders, curtains by applying the translational kinetic energy and vibration energy by uniformly spraying the solution in which the microparticles are dispersed on a substrate transferred at a constant speed. , It can be coated with a strong, uniform and fast adhesion to a substrate such as plastic or polymer.

The second aspect of the present application is to form a matrix-microparticle film complex by coating the microparticles on the surface of the substrate by applying a liquid spray in the solution while passing the substrate through a container containing the microparticle-containing solution. It provides a method for producing a substrate-fine particle membrane composite using a spray, including.

In one embodiment of the present application, two or more containers containing the microparticle-containing solution are connected in series, and each of the containers includes the same or different microparticles, and the substrate is the two or more A multi-layer film including two or more microparticle films may be formed on the substrate by sequentially passing through the container containing the microparticle-containing solution and applying the solution spray in each container, but may not be limited thereto. For example, the solvent contained in the microparticle-containing solution may be appropriately selected in consideration of the physicochemical properties of the microparticles and the substrate used such as water or alcohols or organic solvents.

In one embodiment of the present application, the method of manufacturing a substrate-microparticle membrane complex using the submerged spray is achieved when the substrate sequentially passes through the container containing the two or more microparticle-containing solutions. The microparticles may further include drying the coated substrate, but may not be limited thereto.

In one embodiment of the present application, the method of manufacturing the substrate-microparticle membrane composite using the submerged spray may include additional processes such as foaming or embossing after drying or drying the substrate on which the microparticle coating is completed, It is not limited thereto.

In one embodiment of the present application, the method of manufacturing the substrate-microparticle membrane composite using the submerged spray may include performing a foaming process before the substrate is supplied into the microparticle-containing solution, but is not limited thereto. It does not work.

In one embodiment of the present application, the method of manufacturing a substrate-fine particle film composite using the liquid injection may further include plasma treatment to remove impurities remaining on the surface of the substrate where the microparticle coating is completed. However, it may not be limited thereto. For example, the plasma treatment is performed by drying the substrate on which the microparticle coating is completed by using a device such as oxygen plasma or Ar plasma, or plasma treatment on the surface of the substrate after further drying, such as foaming and/or embossing, is completed. By performing it, impurities remaining on the surface of the substrate can be removed.

In one embodiment of the present application, the substrate is used without pretreatment or

Before the substrate is passed into the microparticle-containing solution,

(a) a first linking compound linked to the surface of the substrate, or (b) the first linking compound linked to the surface of the substrate and a third linking compound as an intermediate linking compound linked to the first linking compound Preprocessing;

The microparticles are used without pretreatment, or (c) a second linking compound connected to the surface of the microparticles, or (d) a second linking compound connected to the surface of the microparticles and a linking to the second linking compound As an intermediate linking compound, it is pre-treated in a state that includes a fourth linking compound,

By applying the submerged spray in the solution while passing the substrate through the microparticle-containing solution,

-The untreated substrate is bound to the unpretreated microparticles or to a second linking compound connected to the surface of the microparticles,

-The first linking compound connected to the surface of the pre-treated substrate is bound to the non-pretreated microparticles or to the second linking compound connected to the surface of the microparticles,

-The first linking compound linked to the surface of the substrate and the intermediate linking compound linked to the first linking compound, a third linking compound linked to the surface of the microparticles and a second linking compound linked to the second linking compound As a linking compound, it may be combined with a fourth linking compound, but may not be limited thereto.

In one embodiment of the present application, a method of manufacturing a substrate-fine particle membrane complex using submerged liquid such as underwater spraying, strong translational motion generated by means of underwater spray generating means such as underwater spraying in the microparticle-containing container And vibration can be transmitted to the microparticles to induce and promote the binding of the microparticles to the substrate. For example, by such liquid spraying, it is possible to induce and promote the binding of the microparticles to the substrate that has not been pretreated, and also to induce and promote the following binding:

Binding of the untreated substrate with the untreated microparticles or a second connecting compound connected to the surface of the microparticles;

A first linking compound connected to the surface of the pretreated substrate, a bond with the untreated microparticles or a second linking compound connected to the surface of the microparticles; And,

The first linking compound connected to the surface of the substrate and the intermediate linking compound linked to the first linking compound, a third linking compound, a second linking compound linked to the surface of the microparticles, and an intermediate linking to the second linking compound Combined with a fourth linking compound as a compound.

In one embodiment of the present application, a method of manufacturing a substrate-fine particle membrane complex using submerged liquid such as underwater spraying is a linking compound that does not bind the microparticles to a part of the substrate according to the type of the linking compounds. In the process of spraying in water, the microparticles may be controlled to be attached and coated only to a part of the substrate, but may not be limited thereto.

In one embodiment of the present application, the substrate may be formed of at least one material selected from the group consisting of, but may not be limited to:

1. Substance having a hydroxy group on the surface;

2. a metal bonding with a thiol group (-SH) or an amine group (-NH ₂ );

3. Polymer having a functional group on the surface;

4. Organic semiconductor compound, inorganic semiconductor compound or organic-inorganic semiconductor compound;

5. Porous materials selected from the group consisting of zeolites, zeotype-porous molecular sieves, metal organic framework (MOF) materials, covalent organic framework (COF), and complexes thereof;

6. Natural polymers, synthetic polymers, or conductive polymers that have a hydroxy group on the surface or can be treated to have a hydroxy group; And

7. Fiber having a hydroxy group on the surface or treatable to have a hydroxy group.

For example, the substrate may be formed of at least one material selected from the group consisting of, but may not be limited to:

1. A material having a hydroxyl group on its surface as an oxide containing metal or non-metal elements such as titanium dioxide, titanate, and zinc oxide, alone or in combination of two or more;

2. a metal bonding with a thiol group (-SH) or an amine group (-NH ₂ );

3. Polymer having a functional group on the surface;

4. A semiconductor compound of zinc selenide (ZnSe), gallium arsenide (GaAs) or indium phosphide (InP), or a sulfide, selenium compound or phosphorus compound having semiconductor characteristics;

5. Porous materials selected from the group consisting of zeolites, zeotype-porous molecular sieves, metal organic framework (MOF) materials, covalent organic framework (COF), and complexes thereof;

6. Natural polymers, synthetic polymers, or conductive polymers that have a hydroxy group on the surface or can be treated to have a hydroxy group; And

7. Fiber having a hydroxy group on the surface or treatable to have a hydroxy group.

In one embodiment of the present application, the substrate may include various plastics such as fiber, wallpaper, closet products, blinders, curtains, refrigerator endothelial PVC, PP, PE, etc., but is not limited thereto.

In one embodiment of the present application, the microparticles may be formed by including at least one material selected from the group consisting of, but may not be limited to:

1. zeolite;

2. Zeolite with MFI structure, ZSM-5, silicalite-1, TS-1 or metallo-silicalite-1;

3. Zeolite with MEL structure, ZSM-11, silicalite-2, TS-2 or metallo-silicalite-2;

4. Zeolite A, X, Y, L or beta, mordenite, ferrite, ETS-4 or ETS-10;

5. Mesoporous silica of any one of MCM series, SBA series, MSU series and KIT series;

6. Organic-inorganic composite mesoporous structure or layered material;

7. An organic zeolite in which the metal ion and the ligand are three-dimensionally bound, an organometallic zeolite, or a coordination compound zeolite;

8. Composites containing organic dyes, inorganic dyes, organic-inorganic mixed dyes, luminescent dyes or pigments between the pores of the porous material or between the layers of the layered structure material;

9. Porous materials selected from the group consisting of Metal Organic Framework (MOF) materials, Covalent Organic Framework (COF), and complexes thereof; And

10. Metals (non-limiting examples: Cu, Ag, Au, Pd, Pt, Ni, etc.), metal oxides (non-limiting examples: oxides of elements such as Ti, Zr, Si, etc.), and complexes of these metals and metal oxides.

In one embodiment of the present application, the linking compounds may each independently include a compound derived from one or two or more organic compounds selected from the group consisting of, but may not be limited to:

[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), where R represents a halogen group, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl group and at least one of the three R is a halogen group or An alkoxy group,

L1 is a substituted or unsubstituted C ₁ -C ₁₇ alkyl residue, such as an alkyl, aralkyl or aryl group, which may contain one or more oxygen, nitrogen or sulfur atoms,

X is a halogen group, an isocyanate (-NCO) group, a tosyl group or an azide group,

R'is the same as R, and at least two of the four R'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 salt thereof, carboxylic acid and salt thereof, acid anhydride, epoxy group, aldehyde group, ester group, acrylic group, isocyanate group (-NCO), sugar residue, It is a coordination compound capable of exchanging double bond, triple bond, diene, diyne, alkyl phosphine, alkyl acin and ligand,

Y may be located not only at the end of the linking compound, but also in the middle,

L2(+) represents a functional group having at least one positive charge (+) in 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. ,

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 that may contain one or more oxygen, nitrogen, or sulfur atoms. And HS- is a thiol group.

The intermediate linking compound is fullerene (C ₆₀ , C ₇₀ ), carbon nanotube, α,ω-dialdehyde, dicarboxylic acid, dicarboxylic acid anhydride, amine-dendrimer, polyethyleneimine, α,ω-diamine, metal porphyrin and M( Saline) is a complex compound (M is cobalt, nickel, chromium, manganese or iron, and saline is a compound selected from the group consisting of N,N'-bis(salicylidene)ethylenediamine).

In one embodiment of the present application, the temperature of the microparticle-containing solution may be adjusted to about 0 °C to about 100 °C, but may not be limited thereto.

In one embodiment of the present application, the temperature of the container containing the microparticle-containing solution and the external storage unit may be adjusted to about 0°C to about 100°C, but may not be limited thereto.

In one embodiment of the present application, the substrate may include fibers, wallpaper, closet products, blinders, curtains, plastics, or polymers, but may not be limited thereto.

According to the exemplary embodiments of the present application, volatile organic solvents such as formaldehyde, benzene, toluene, and the like, exhibiting sick house syndrome by uniformly and strongly coating fine particles such as zeolite on one or both surfaces of a substrate such as a fiber, wallpaper, blinder, curtain, and the like. It can be useful to adsorb radioactive iodine, a mustard gas, phosgen, sarin, chlorine gas, and radioactive gas, which are chemical mass destruction gases during the war.

Hereinafter, the present application will be described in more detail by examples, but the present application is not limited thereto.

[ Example ]

< Example 1>

Zeolite microparticles were attached to the blinder by underwater spraying using a submerged microparticle attachment device shown in FIG. 2A, and the results are shown in FIGS. 4 to 7.

Figure 4, in one embodiment of the present application, shows an SEM image of a blinder with zeolite attached using an underwater spray method, and a SEM image of a blinder without zeolite as a comparative example.

5 shows, in one embodiment of the present application, an SEM image of a blinder with zeolite attached using an underwater spray method.

Figure 6, in one embodiment of the present application, shows an SEM image of a blinder to which a zeolite is attached using an underwater spray method.

7 shows, in one embodiment of the present application, a SEM image after washing the blinder to which the zeolite is attached with an ultrasonic cleaner for 20 seconds.

As can be seen from the SEM images of FIGS. 4 to 7, in this embodiment, it was confirmed that the microparticles of the zeolite were attached to the surface of the bleed using the underwater spraying method, in particular, as shown in FIG. Likewise, by subjecting the microparticles of the zeolite to ultrasonic treatment after removing the microparticles of the zeolite which are excessively present on the blind surface, the microparticles of the zeolite can be uniformly attached to the surface of the bleed.

< Example 2>

Zeolite microparticles were attached to the wallpaper by underwater spraying using the underwater spray type microparticle attachment device shown in FIG. 2A, and the results are shown in FIGS. 8 to 11.

8 shows, in one embodiment of the present application, an SEM image of a wallpaper with zeolite attached using an underwater spray method, and a SEM image of a wallpaper without zeolite attached as a comparative example.

9 shows, in one embodiment of the present application, an SEM image of a wallpaper with zeolite attached using an underwater spray method.

Figure 10, in one embodiment of the present application, shows a SEM image after 20 seconds of washing the wallpaper with a zeolite attached to an ultrasonic cleaner.

11 shows, in one embodiment of the present application, SEM images after 20 seconds of washing the wallpaper with zeolite attached with an ultrasonic cleaner.

As can be seen from the SEM images of FIGS. 8 to 11, in the present embodiment, it was confirmed that the microparticles of the zeolite were attached to the surface of the bleed using the underwater spraying method. In particular, FIGS. 10 and 11 As shown in the above, it was possible to uniformly adhere the microparticles of the zeolite to the surface of the bleed by removing the microparticles of the zeolite excessively present on the blind surface by ultrasonic treatment after coating the microparticles of the zeolite.

The above description of the present application is for illustrative purposes, and those skilled in the art to which the present application pertains will understand that it is possible to easily modify to 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 illustrative 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 claims below, rather than the detailed description, and it should be interpreted that all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof are included in the scope of the present application.

10: 1st substrate transfer part 10': 2nd substrate transfer part
20: microparticle-containing solution 21: container containing the microparticle-containing solution
30: spray nozzle 40: reflector and support
50: removal roller 70: roller
100: coating unit 200: drying unit
300: foaming unit 400: embossing unit
110: temperature control unit A 120: temperature control unit B
130: external storage

Claims (28)

A first transfer unit for transferring the substrate;
A coating unit coating the substrate continuously transferred from the first transfer unit by microparticles; And
A second transfer unit for recovering the coated substrate from the coating unit
Including, in-spray injection microparticle coating apparatus,
The coating unit,
A container containing a microparticle-containing solution;
A spray nozzle for coating the microparticles on the substrate by spraying the microparticle-containing solution toward the substrate in a container containing the microparticle-containing solution;
A reflector and a support to prevent the substrate from being pushed or deformed from the sprayed solution; And
Removal roller for removing excess microparticles or the microparticle-containing solution sprayed on the substrate
That includes,
Liquid injection type microparticle coating device.
According to claim 1,
The spray nozzle is located in the inner portion of the container containing the microparticle-containing solution, liquid injection type microparticle coating apparatus.
According to claim 2,
The spray nozzle is located on both sides of the inner wall of the container containing the microparticle-containing solution and / or the lower portion, the spray-type microparticle coating apparatus in liquid.
According to claim 2,
The spray nozzle is disposed in two or more rows along the transport direction of the substrate, the liquid injection type microparticle coating apparatus.
According to claim 1,
The microparticles included in each of the containers containing the microparticle-containing solution contained in each of the coating units and connected to two or more coating units are the same or different from each other, or
Two or more containers containing the microparticle-containing solution are provided in the coating part, and the microparticles included in each of the containers are the same or different from each other.
Liquid injection type microparticle coating device.
According to claim 1,
It further includes a temperature control unit A for controlling the temperature of the microparticle-containing solution in the coating unit, liquid injection type microparticle coating apparatus.
According to claim 1,
Further comprising an external reservoir for supplying the solution to the container containing the microparticle-containing solution in the coating part and recovering the used solution from the container containing the microparticle-containing solution to circulate the solution. Fine particle coating device.
The method of claim 7,
The external storage unit is provided with a temperature control unit B, liquid injection type microparticle coating apparatus.
The method of claim 7,
The temperature of the external storage unit is controlled by a temperature control unit A for controlling the temperature of the microparticle-containing solution in the coating unit, the liquid injection type microparticle coating apparatus.
According to claim 1,
Further comprising a drying unit disposed between the coating unit and the second transfer unit, liquid injection type microparticle coating apparatus.
The method of claim 10,
Further comprising a foaming unit and / or embossing portion disposed between the drying unit and the second transfer unit, the liquid injection type microparticle coating apparatus.
According to claim 1,
Further comprising a foam portion disposed between the first transfer portion and the coating portion, liquid injection type microparticle coating apparatus.
The method of claim 10,
In addition to the spray nozzle, the removal roller and the chamber surrounding the drying unit, the liquid injection type fine particle coating apparatus.
According to claim 1,
The microparticles containing a functional group that can be attached to the surface of the substrate, the liquid injection type microparticle coating apparatus.
According to claim 1,
In order to remove the impurities remaining on the surface of the substrate further comprises a plasma treatment portion for plasma treatment in front of the second transfer portion, the liquid injection type microparticle coating apparatus.
According to claim 1,
The substrate is a fiber, wallpaper, closet products, blinders, curtains, plastics, or containing a polymer, liquid injection type microparticle coating device.
Coating the microparticles on the surface of the substrate to form a matrix-microparticle film composite by applying a liquid jet in the solution while passing the substrate through a container containing the microparticle-containing solution
A method of manufacturing a substrate-fine particle membrane complex using spraying in liquid.
The method of claim 17,
Two or more containers containing the microparticle-containing solution are connected in series, and each of the containers includes the same or different microparticles,
A multi-layered film comprising two or more microparticle films is formed on the substrate by sequentially passing the container containing the two or more microparticle-containing solutions and applying the solution spray in each container.
Method of manufacturing a substrate-fine particle membrane complex using liquid spray.
The method of claim 18,
Substrate-microparticle membrane using submerged spray, further comprising drying the substrate coated with the microparticles between each container when the substrate sequentially passes through the container containing the two or more microparticle-containing solutions. Method of manufacturing a complex.
The method of claim 17,
The substrate can be used without pretreatment or
Before the substrate is passed into the microparticle-containing solution,
(a) a first linking compound linked to the surface of the substrate, or (b) the first linking compound linked to the surface of the substrate and a third linking compound as an intermediate linking compound linked to the first linking compound Preprocessing;
The microparticles are used without pretreatment, or (c) a second linking compound connected to the surface of the microparticles, or (d) a second linking compound connected to the surface of the microparticles and a linking to the second linking compound As an intermediate linking compound, it is pre-treated with a fourth linking compound,
By applying the submerged spray in the solution while passing the substrate through the microparticle-containing solution,
-The untreated substrate is bound to the unpretreated microparticles or to a second linking compound connected to the surface of the microparticles,
-The first linking compound connected to the surface of the pre-treated substrate is bound to the non-pretreated microparticles or to the second linking compound connected to the surface of the microparticles,
-The first linking compound linked to the surface of the substrate and the intermediate linking compound linked to the first linking compound, a third linking compound linked to the surface of the microparticles, a second linking compound and the second linking compound As a linking compound, it is bound to a fourth linking compound.
Method of manufacturing a substrate-fine particle membrane complex using liquid spray.
The method of claim 17,
The substrate is formed by including one or more substances selected from the group consisting of, Method of producing a substrate-fine particle membrane complex using a liquid injection:
1. Substance having a hydroxy group on the surface;
2. a metal bonding with a thiol group (-SH) or an amine group (-NH ₂ );
3. Polymer having a functional group on the surface;
4. Organic semiconductor compound, inorganic semiconductor compound or organic-inorganic semiconductor compound;
5. Porous materials selected from the group consisting of zeolites, zeotype-porous molecular sieves, metal organic framework (MOF) materials, covalent organic framework (COF), and complexes thereof;
6. Natural polymers, synthetic polymers, or conductive polymers that have a hydroxy group on the surface or can be treated to have a hydroxy group; And
7. Fiber having a hydroxy group on the surface or treatable to have a hydroxy group.
The method of claim 17,
The microparticles are formed by including at least one material selected from the group consisting of, Method of producing a substrate-fine particle membrane complex using liquid spray:
1. zeolite;
2. Zeolite with MFI structure, ZSM-5, silicalite-1, TS-1 or metallo-silicalite-1;
3. Zeolites with MEL structure, ZSM-11, silicalite-2, TS-2 or metallo-silicalite-2;
4. Zeolite A, X, Y, L or beta, mordenite, ferrite, ETS-4 or ETS-10;
5. Mesoporous silica of any one of MCM series, SBA series, MSU series and KIT series;
6. Organic-inorganic composite mesoporous structure or layered material;
7. An organic zeolite in which the metal ion and the ligand are three-dimensionally bound, an organometallic zeolite, or a coordination compound zeolite;
8. Composites containing organic dyes, inorganic dyes, organic-inorganic mixed dyes, luminescent dyes or pigments between the pores of the porous material or between the layers of the layered structure material;
9. Porous materials selected from the group consisting of Metal Organic Framework (MOF) materials, Covalent Organic Framework (COF), and complexes thereof; And
10. Metals, metal oxides, and complexes of metals and metal oxides.
The method of claim 20,
Each of the linking compounds independently comprises a compound derived from one or two or more organic compounds selected from the group consisting of: Method for producing a substrate-fine particle membrane complex using liquid spray:
[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), where R is a halogen group, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkyl group and at least one of the three Rs is a halogen or alkoxy group ,
L1 is a substituted or unsubstituted C ₁ -C ₁₇ alkyl residue, such as an alkyl, aralkyl or aryl group, which may contain one or more oxygen, nitrogen or sulfur atoms,
X is a halogen group, an isocyanate (-NCO) group, a tosyl group or an azide group,
R'is the same as R, and at least two of the four R'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 salt thereof, carboxylic acid and salt thereof, acid anhydride, epoxy group, aldehyde group, ester group, acrylic group, isocyanate group (-NCO), sugar residue, It is a coordination compound capable of exchanging double bonds, triple bonds, dienes, diynes, alkyl phosphine, alkyl ynes, and ligands, and Y may be located in the middle as well as the end of the linking compound,
L2(+) represents a functional group having at least one positive charge (+) in 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. ,
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 that may contain one or more oxygen, nitrogen, or sulfur atoms. and,
HS- is a thiol group.
The method of claim 17,
The microparticle-containing solution is circulated by an external storage unit for supplying the microparticle-containing solution into a container containing the microparticle-containing solution and recovering the used microparticle-containing solution. Method of manufacturing a substrate-microparticle membrane complex to be used.
The method of claim 17,
The temperature of the microparticle-containing solution is to be adjusted to 0 ℃ to 100 ℃, the method of manufacturing a substrate-fine particle membrane complex using a liquid spray.
The method of claim 24,
The temperature of the container containing the microparticle-containing solution and the temperature of the external storage unit is controlled to 0°C to 100°C, wherein the substrate-fine particle film composite is manufactured by using liquid spray.
The method of claim 17,
A method of manufacturing a substrate-fine particle film composite using liquid spray, further comprising plasma treatment for plasma treatment to remove impurities remaining on the surface of the substrate on which the microparticles are coated.
The method of claim 17,
The substrate is a fiber, wallpaper, closet products, blinders, curtains, plastics, or containing a polymer, a method of manufacturing a substrate-fine particle membrane composite using liquid spray.

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