WO2018203670A1

WO2018203670A1 - Microparticle coating apparatus using submerged spraying, and method for preparing substrate-microparticle film composite by using same

Info

Publication number: WO2018203670A1
Application number: PCT/KR2018/005107
Authority: WO
Inventors: 윤영민
Original assignee: 주식회사 지오엔
Priority date: 2017-05-02
Filing date: 2018-05-02
Publication date: 2018-11-08
Also published as: KR102125317B1; KR20180122299A

Abstract

Provided are: a method for preparing a substrate-microparticle film composite by using submerged spraying such as underwater spraying; and a submerged spraying-type microparticle coating apparatus to be used therefor.

Description

Apparatus for fine particle coating using submerged jetting and method for preparing substrate-microparticle film composite using same

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

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

In the simplest method, the substrate was immersed 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. This method is to control the degree of dispersion of the zeolite by controlling the rate of removing the zeolite from the turbid liquid, so that it is difficult to form a uniform monolayer film of the zeolite particles, and since the zeolite is simply physically adsorbed to the substrate, the particles are separated from the substrate. It tended to break away easily.

As another conventional method, (1) a covalent bond between a substrate and a linking compound (intermediate 1), a covalent bond between a molecular sieve particle and a linking compound (intermediate 2), and then the intermediate 1 and the A method of forming a substrate-molecular sieve membrane complex by covalently binding, ionizing, or coordinating intermediate 2, (2) covalently bonding one end of the linking compound with the substrate or molecular sieve particles and the other end of the linking compound A method of directly binding to a molecular sieve to form a substrate-molecular sieve membrane complex, (3) inserting an intermediate linking compound between intermediate 1 and intermediate 2 to control the length between the substrate and molecular sieve particles while controlling the length of the substrate-molecular sieve membrane complex (4) repeating the above (1) to (3) to form a multi-layer molecular sieve film on the substrate, etc., which is a substrate-molecular sieve film complex Significant contributions have been made to the application of new materials, but energy efficiency is achieved because simple reflux method is used to bond substrate and linking compound, molecular sieve particle and linking compound, linking compound and linking compound and linking compound and intermediate linking compound. And adhesion rate is low, there is a problem that the density between the adhered zeolite particles is lowered, the bond strength between the attached zeolite and the substrate is weak. In addition, mass production was difficult due to the limitation of simple reflux.

In addition, since the proposed methods attach the zeolite to the substrate (fabric, etc.) by a chemical method, a separate process for this takes a lot of treatment costs according to the design, and the process must be performed separately from the substrate processing process. And there was a problem that the process efficiency is lowered according to the process time.

[선행기술문헌][Preceding technical literature]

(Patent Document) Korean Patent Registration Publication No. 10-0395902

However, the problem to be solved by the present application is not limited to the above-mentioned problem, 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 a submerged spray type microparticle coating apparatus comprising:

A first transfer part for transferring the substrate;

A coating unit coating the substrate continuously transferred from the transfer unit by fine particles; And

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

Including, the submerged spray type 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 the 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 of the microparticles or the microparticle-containing solution sprayed on the substrate

It is to include.

A second aspect of the present application is to form a substrate-microparticle film complex by coating the microparticles on the surface of the substrate by applying a submerged jet in the solution while passing the substrate into the container containing the microparticle-containing solution Provided is a method for producing a substrate-microparticle film composite using a liquid injection.

In accordance with embodiments of the present invention, a submerged spray type microparticle coating apparatus for producing a substrate-microparticle film composite using submerged spraying such as underwater spraying and a method of preparing the substrate-microparticle film composite using submerged spraying using the apparatus This is provided.

According to the embodiments of the present invention, by using a submerged injection, such as underwater injection, by applying the translational kinetic energy and vibration energy to the substrate and the linking compound, microparticles and the linking compound, linking compound and the linking compound or linking compound instead of simple reflux By inducing covalent, ionic, coordinating or hydrogen bonding between intermediate linking compounds, not only can the substrate and microparticles be bonded in a variety of ways, but it also saves time and has significantly higher adhesion rates, adhesion strengths, adhesion levels and densities. In this case, when the substrate to which the linking compound is bound is mixed with the substrate to which the linking compound is not mixed, the microparticles can be selectively attached to only the substrate to which the linking compound is bound, thereby improving the mass production of the substrate-microparticle film complex. have.

According to the embodiments of the present invention, a submerged spray type microparticle coating apparatus such as an underwater spray and a method of manufacturing a substrate-microparticle film composite using submerged spray using the apparatus may include fibers, wallpaper, closet products, blinds, curtains and plastics. A substrate or substrate for transporting the substrate, a plurality of injection nozzles for injecting microparticles toward the substrate, a reflector and support for preventing the substrate from being pushed or deformed from the sprayed solution, and an excessive aqueous solution attached to the fibers. And a container for containing the solution in which the fine particles are dispersed. As a result, evenly spraying the solution in which the fine particles are dispersed on the substrate to be transported at a constant speed may apply translational kinetic energy and vibration energy so that the fine particles can be strongly and uniformly and quickly attached to the substrate.

According to the embodiments of the present invention, formaldehyde exhibiting a sick house syndrome by uniformly and strongly binding microparticles such as zeola art to one or both surfaces of a substrate such as a fiber, wallpaper, closet product, blind, curtain, plastic, or polymer. Volatile organic solvents such as benzene, toluene, and radioactive iodine, which are chemical gas killing gases, mustard gas, phosgen, sarin, chlorine gas and radioactive gas. .

Figure 1a, in one embodiment of the present application, is a block diagram of a submerged spray type microparticle coating apparatus.

Figure 1b, in one embodiment of the present application, is a block diagram of a submerged spray type microparticle coating apparatus.

Figure 1c, in one embodiment of the present application, is a block diagram of a submerged spray type microparticle coating apparatus.

Figure 2a, in one embodiment of the present application, is a schematic diagram of a submerged spray type microparticle coating apparatus.

Figure 2b is, in one embodiment of the present application, a schematic diagram of a submerged spray type microparticle coating apparatus.

Figure 3a, in one embodiment of the present application, is a block diagram of a submerged spray type microparticle coating apparatus.

Figure 3b is, in one embodiment of the present application, a block diagram of a submerged spray type microparticle coating apparatus.

Figure 4 shows an SEM image of a zeolite-attached blinder using an underwater spray method, and an SEM image of a zeolite-free blinder as a comparative example in one embodiment of the present application.

FIG. 5 shows an SEM image of a blinder to which zeolite is attached using an underwater spray method in one embodiment of the present application.

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

FIG. 7 shows an SEM image after washing a zeolite-attached blinder with an ultrasonic cleaner for 20 seconds in one embodiment of the present disclosure.

FIG. 8 shows an SEM image of a wallpaper on which zeolite is attached by using an underwater spray method and an SEM image of wallpaper on which zeolite is not attached as a comparative example.

FIG. 9 shows an SEM image of a wallpaper to which zeolite is attached using the underwater spray method in one embodiment of the present application.

FIG. 10 is a SEM image after washing a zeolite-attached wallpaper with an ultrasonic cleaner for 20 seconds in one embodiment of the present disclosure.

FIG. 11 is a SEM image after washing a zeolite-attached wallpaper with an ultrasonic cleaner for 20 seconds in one embodiment of the present disclosure.

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 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.

A first transfer part for transferring the substrate;

Including, the submerged spray type microparticle coating apparatus,

The coating unit,

A container containing a microparticle-containing solution;

It is to include.

In one embodiment of the invention, the injection nozzle is to be located on the inner side of the container containing the microparticle-containing solution.

In one embodiment of the present application, the injection nozzle may be located at both side walls and / or the lower side of the inner side of the container containing the microparticle-containing solution.

Referring to Figure 1a, in one embodiment of the present application, the submerged spray-type microparticle coating apparatus, the first transfer unit 10 for transporting the substrate; A coating part 100 for coating the substrate continuously transferred from the first transfer part by fine particles; And a second transfer part 10 ′ for recovering the coated substrate from the coating part, but may not be limited thereto.

Referring to FIG. 1B, in the embodiment of the present application, the submerged spray type microparticle coating apparatus further includes a temperature controller A 110 for controlling a temperature of the microparticle-containing solution in the coating unit. It may be, but may not be limited thereto. For example, the temperature of the microparticle-containing solution may be adjusted to about 0 ° C. to about 100 ° C. by the temperature controller A 110, but may not be limited thereto.

Referring to FIG. 1C, in one embodiment of the present application, the solution is supplied to a container containing the microparticle-containing solution in the coating part 100 and the solution used from the container containing the microparticle-containing solution. It may be to include an additional external storage unit 130 to circulate the solution by recovering, but may not be limited thereto.

Referring to FIG. 1C, in the exemplary embodiment of the present application, the external storage unit 130 may be provided with a temperature controller 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 controller B 120, but may not be limited thereto.

Referring to FIG. 1C, in another embodiment of the present disclosure, the temperature of the external storage unit 130 is controlled by a temperature controller A 110 for controlling the temperature of the microparticle-containing solution in the coating unit 100. It may be adjusted by, but may not be limited thereto.

2A and 2B, the liquid-injection type microparticle coating apparatus according to one embodiment of the present application includes a first transfer part 10 for transferring a substrate S; A container 21 containing a microparticle-containing solution 20, wherein the microparticles contain functional groups capable of adhering 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 adhered to the substrate; And a second transfer part 10 ′ which recovers the substrate that has passed through the removal roller, but is not limited thereto. One or more of the spray nozzles 30 may be located in the interior wall of the vessel 21 containing the microparticle-containing solution 20 and in the solution (FIG. 1A), or one or more of the spray nozzles 30 may be It may be located on the inner wall of the vessel 21 containing the microparticle-containing solution 20 (FIG. 1B), but the present 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 injection nozzle may be arranged 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 two or more coatings are connected and the microparticles contained in each of the containers containing the microparticle-containing solution contained in each of the coating is the same or different from each other, or the coating At least two containers containing the microparticle-containing solution are provided in the container, and the microparticles contained in each of the containers are the same or different from each other.

It may be, but may not be limited thereto. For example, the solvent included 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 injection nozzle may be to spray the microparticles in the range of about 0.01 g to about 1 g per m ² of the substrate, but may not be limited thereto.

In one embodiment of the present application, the microparticles may contain a functional group 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, but is not limited to, fibers, wallpaper, closet products, blinds, curtains, plastics, or polymers.

3A and 3B, in one embodiment of the present application, the submerged spray type microparticle coating apparatus may include a drying unit 200 disposed between the coating unit 100 and the second transfer unit 10 ′. It may be to include an additional, but may not be limited thereto.

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

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

Referring to FIG. 3A, in one embodiment of the present disclosure, the submerged spray type microparticle coating apparatus may include a foam part 300 and / or disposed between the drying part 200 and the second transfer part 10 ′. The embossing unit 400 may be additionally included, but may not be limited thereto.

Referring to FIG. 3B, in one embodiment of the present application, the submerged spray type microparticle coating apparatus further includes a foam part 300 disposed between the first transfer part 10 and the coating part 100. It may be, but may not be limited thereto.

In one embodiment of the present application, the submerged spray type microparticle coating apparatus, to remove impurities remaining on the surface of the substrate after the completion of the further process, such as drying or foaming, embossing the substrate is completed the microparticle coating is complete In order to include a plasma processing unit for performing a plasma treatment in front of the second transfer unit, but may not be limited thereto. The plasma processing unit may be provided with an apparatus such as an oxygen plasma or an Ar plasma to dry the substrate on which the fine particle coating is completed or to perform plasma treatment on the surface of the substrate on which the additional processes such as foaming and embossing are completed after drying. Residual impurities and the like can be removed.

By using the liquid-injection type microparticle attachment device, the microparticles are uniformly sprayed onto the substrate to be transported at a constant speed to apply translational kinetic and vibrational energy so that the microparticles are fibers, wallpaper, closet products, blinds, curtains. Strong, uniform and fast adhesion coating on substrates such as, plastics, or polymers.

In one embodiment of the present invention, two or more vessels containing the microparticle-containing solution are connected in series, each of the vessels comprises the same or different microparticles from each other, the substrate is the two or more By sequentially passing through a container containing the microparticle-containing solution and applying the solution spray in each container, a multilayer film including two or more microparticle films may be formed on the substrate, but may not be limited thereto. For example, the solvent included 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 invention, the method for producing a substrate-microparticle membrane composite using the submerged injection, the substrate is sequentially passed through each container containing the two or more microparticle-containing solutions It may further include drying the substrate coated with the microparticles, but may not be limited thereto.

In one embodiment of the present application, the method for producing a substrate-microparticle film composite using the submerged spray may include an additional process, such as after drying the substrate on which the fine particle coating is completed or after drying, foaming, embossing, It is not limited to this.

In one embodiment of the present application, the method for preparing a substrate-microparticle film composite using the liquid injection may include performing a foaming process before the substrate is supplied into the microparticle-containing solution, but is not limited thereto. It doesn't happen.

In one embodiment of the present application, the method of manufacturing a substrate-microparticle film composite using the submerged injection may further include plasma treatment to remove impurities and the like remaining on the surface of the substrate on which the microparticle coating is completed. However, this may not be limited. For example, the plasma treatment may be performed using a device such as an oxygen plasma or an Ar plasma to dry the substrate on which the microparticle coating is completed, or to perform a plasma treatment on the surface of the substrate on which the further processing such as foaming and / or embossing is completed after drying. By carrying out, impurities remaining on the surface of the substrate can be removed.

In one embodiment of the invention, 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) a first linking compound linked to the surface of the substrate and an intermediate linking compound linked to the first linking compound, and including a third linking compound. To be pretreated;

The microparticles may be used without pretreatment, or (c) comprise 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 linked to the second linking compound. As intermediate linking compound, it is pretreated with the fourth linking compound,

By applying the submerged jet in the solution while passing the substrate into 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 linked to the surface of the pretreated substrate is bound to the unpretreated microparticles or to a second linking compound linked to the surface of the microparticles,

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

In one embodiment of the present application, the method for producing a substrate-microparticle membrane complex using a liquid spray, such as the water spray, in the microparticle-containing vessel strong translational movement occurred in the liquid spray generating means such as the water spray Excessive vibration may be transmitted to the microparticles to induce and promote binding of the microparticles to the substrate. For example, such liquid spraying can induce and promote binding of the microparticles to the substrate that has not been pretreated, and can also induce and promote the following binding:

Binding to the untreated substrate and the untreated microparticles or to a second linking compound connected to the surface of the microparticles;

A first linking compound connected to the surface of the pretreated substrate and a second linking compound connected to the unpretreated microparticles or a surface connected to the surface of the microparticles; And,

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

In one embodiment of the present application, the method for producing a substrate-microparticle membrane complex using a liquid spray, such as in the water spray, a linking compound that does not bind the microparticles to a part of the substrate depending on the type of the linking compounds By binding to the microparticles in the process of liquid spray can be adjusted to adhere to only a portion of the substrate, but may not be limited thereto.

In one embodiment of the present disclosure, the substrate may be formed by including one or more materials selected from the group consisting of, but may not be limited thereto:

1. a substance having a hydroxy group on its surface;

2. a metal bonded to a thiol group (-SH) or an amine group (-NH ₂ );

3. A polymer having a functional group on the surface;

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

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

6. Natural polymers, synthetic polymers or conductive polymers having a hydroxy group on the surface or capable of being treated to have a hydroxy group; And

7. A fiber having a hydroxy group on its surface or treatable to have a hydroxy group.

For example, the substrate may be formed by including one or more materials selected from the group consisting of, but may not be limited thereto:

1. A substance having a hydroxy group on its surface as an oxide containing only one or two or more metals and nonmetallic elements such as titanium dioxide, titanate and zinc oxide;

2. a metal bonded to a thiol group (-SH) or an amine group (-NH ₂ );

3. polymers having functional groups on the surface;

4. Semiconductor compounds of zinc selenide (ZnSe), gallium arsenide (GaAs) or indium phosphide (InP), or sulfides, selenium compounds or phosphorus compounds having semiconductor characteristics;

In one embodiment of the present application, the substrate may include various plastics such as fibers, wallpaper, closet products, blinds, curtains, refrigerators, PVC, PP, PE, but may not be limited thereto.

In one embodiment of the present application, the microparticles may be formed including one or more materials selected from the group consisting of, but may not be limited thereto:

1. zeolite;

2. Zeolite, ZSM-5, Silicalite-1, TS-1 or Metallo-Silicalite-1 with MFI structure;

3. Zeolite, ZSM-11, Silicalite-2, TS-2 or Metallo-Silicalite-2 with MEL structure;

4. Zeolite A, X, Y, L or Beta, Mordenite, Ferrierite, ETS-4 or ETS-10;

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

6. organic-inorganic composite mesoporous structures or layered materials;

7. Organic zeolite, organometallic zeolite or coordination compound zeolite in which metal ion and ligand are three-dimensionally bound;

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

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

10. Metals (including but not limited to Cu, Ag, Au, Pd, Pt, Ni, etc.), metal oxides (such as, but not limited to, oxides of elements such as Ti, Zr, Si, etc.), and composites 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 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 an alkyl, aralkyl or aryl group which is substituted or unsubstituted C ₁ -C ₁₇ and may comprise 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, 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 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 compound is a fullerene (C ₆₀ , C ₇₀ ), carbon nanotubes, α, ω-dialdehyde, dicarboxylic acid, dicarboxylic anhydride, amine-dendrimer, polyethyleneimine, α, ω-diamine, metal porphyrin 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, 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 vessel containing the microparticle-containing solution and the external storage may be adjusted to about 0 ℃ to about 100 ℃, but may not be limited thereto.

According to the embodiments of the present invention, a volatile organic solvent such as formaldehyde, benzene, toluene, etc., which exhibits a sick house syndrome by uniformly and strongly binding microparticles such as zeolite on one or both surfaces of a substrate such as fibers, wallpaper, blinds, curtains, and the like, and It can be useful for adsorbing chemical mass destruction gas mustard gas, phosgen, sarin, chlorine gas and radioactive iodine.

[부호의 설명][Description of the code]

10: first substrate transfer portion 10 ': second substrate transfer portion

20: microparticle-containing solution 21: container for microparticle-containing solution

30: spray nozzle 40: reflector and support

50: removal roller 70: roller

100: coating part 200: drying part

300: foaming part 400: embossing part

110: temperature control unit A 120: temperature control unit B

130: external storage unit

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[실시예]EXAMPLE

<실시예 1><Example 1>

Zeolite microparticles were attached to the blind by using the liquid-injection type microparticle attachment apparatus shown in FIG. 2A, and the results are shown in FIGS. 4 to 7.

As can be seen from the SEM images of FIGS. 4 to 7, in the present embodiment, it was confirmed that the microparticles of the zeolite adhered to the surface of the blade using the above-mentioned water spraying method. In particular, as shown in FIG. Likewise, by performing an ultrasonic treatment after the microparticles of the zeolite, the microparticles of the zeolite that are excessively present on the blind surface may be removed to uniformly adhere the microparticles of the zeolite to the blade surface.

<실시예 2><Example 2>

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

FIG. 10 is a SEM image after washing a zeolite-attached wallpaper with an ultrasonic cleaner for 20 seconds in one embodiment of the present application.

FIG. 11 is a SEM image after washing a zeolite-attached wallpaper with an ultrasonic cleaner for 20 seconds in one embodiment of the present application.

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 blade using the above-mentioned water spraying method. In particular, FIGS. 10 and 11 As shown in FIG. 2, the microparticles of the zeolite could be uniformly attached to the surface of the blade by removing the microparticles of the zeolite that are excessively present on the blind surface by performing an ultrasonic treatment after coating the microparticles of the zeolite.

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 first transfer part for transferring the substrate;

A coating unit coating the substrate continuously transferred from the transfer unit by fine particles; And

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

Including, the submerged spray type 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 the 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 of the microparticles or the microparticle-containing solution sprayed on the substrate

To include,

Submerged spray type microparticle coating device.
The method of claim 1,

And the spray nozzle is located inside the container containing the microparticle-containing solution.
The method of claim 2,

The spray nozzle is a submerged spray type microparticle coating apparatus is located on both side walls and / or the lower side of the inner portion of the container containing the microparticle-containing solution.
The method of claim 2,

The spray nozzles are arranged in two or more rows along the transport direction of the substrate, submerged spray type microparticle coating apparatus.
The method of claim 1,

The two or more coatings are connected and the microparticles contained in each of the containers containing the microparticle-containing solution included in each of the coatings are the same or different from each other, or

At least two 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.

Submerged spray type microparticle coating device.
The method of claim 1,

The apparatus further comprises a temperature control unit A for controlling the temperature of the microparticle-containing solution in the coating portion, submerged spray type microparticle coating apparatus.
The method of claim 1,

Injecting the solution to the container containing the microparticle-containing solution in the coating portion and further comprising an external reservoir for recovering the used solution from the container containing the microparticle-containing solution to circulate the solution Microparticle coating apparatus.
The method of claim 7, wherein

The external storage unit is provided with a temperature control unit B, submerged spray type microparticle coating apparatus.
The method of claim 7, wherein

The temperature of the external storage is controlled by a temperature control unit A for controlling the temperature of the microparticle-containing solution in the coating, submerged spray type microparticle coating apparatus.
The method of claim 1,

And a drying part disposed between the coating part and the second conveying part.
The method of claim 1,

Submerged spray type microparticle coating apparatus further comprising a foam and / or embossed portion disposed between the drying unit and the second conveying unit.
The method of claim 1,

Injecting micro-particle coating apparatus further comprising a foam disposed between the first transfer portion and the coating.
The method of claim 1,

And a chamber surrounding the spray nozzle, the removal roller, and the drying unit.
The method of claim 1,

The microparticles will contain a functional group that can adhere to the surface of the substrate, submerged spray type microparticle coating apparatus.
The method of claim 1,

And a plasma treatment part for performing a plasma treatment on the front end of the second transfer part to remove impurities remaining on the surface of the substrate.
The method of claim 1,

The substrate is a liquid-injection type microparticle coating apparatus that contains the fibers, wallpaper, closet products, blinds, curtains, plastics, or polymers.
Coating the microparticles on the surface of the substrate to form a substrate-microparticle film complex by applying a submerged jet in the solution while passing the substrate through the container containing the microparticle-containing solution

A method for producing a substrate-microparticle film composite using a liquid injection, comprising a.
The method of claim 17,

Two or more vessels containing the microparticle-containing solution are connected in series, each vessel containing the same or different fine particles,

Wherein the substrate is sequentially passed through the container containing the two or more microparticle-containing solutions and by applying the solution spray in each container, a multilayer film comprising two or more microparticle films is formed on the substrate,

A method for producing a substrate-microparticle membrane composite using submerged jetting.
The method of claim 18,

Further comprising drying the substrate coated with the microparticles between each vessel as the substrate sequentially passes through a vessel containing the two or more microparticle-containing solutions. Method for preparing a composite.
The method of claim 17,

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) a first linking compound linked to the surface of the substrate and an intermediate linking compound linked to the first linking compound, and including a third linking compound. To be pretreated;

The microparticles may be used without pretreatment, or (c) comprise 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 linked to the second linking compound. As intermediate linking compound, it is pretreated with the fourth linking compound,

By applying the submerged jet in the solution while passing the substrate into 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 linked to the surface of the pretreated substrate is bound to the unpretreated microparticles or to a second linking compound linked to the surface of the microparticles,

The first linking compound connected to the surface of the substrate and the intermediate linking compound linked to the first linking compound, wherein a third linking compound is linked to the second linking compound and the second linking compound linked to the surface of the microparticle. As a linking compound combined with a fourth linking compound

A method for producing a substrate-microparticle membrane composite using submerged jetting.
The method of claim 17,

The substrate is formed by including one or more materials selected from the group consisting of, a method for producing a substrate-microparticle membrane complex using submerged injection:

1. a substance having a hydroxy group on its surface;

2. a metal bonded to a thiol group (-SH) or an amine group (-NH 2 );

3. A polymer having a functional group on the surface;

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

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

6. Natural polymers, synthetic polymers or conductive polymers having a hydroxy group on the surface or capable of being treated to have a hydroxy group; And

7. A fiber having a hydroxy group on its surface or treatable to have a hydroxy group.
The method of claim 17,

The microparticles are formed by including one or more substances selected from the group consisting of, a method for producing a substrate-microparticle membrane complex using submerged injection:

1. zeolite;

2. Zeolite, ZSM-5, Silicalite-1, TS-1 or Metallo-Silicalite-1 with MFI structure;

3. Zeolite, ZSM-11, Silicalite-2, TS-2 or Metallo-Silicalite-2 with MEL structure;

4. Zeolite A, X, Y, L or Beta, Mordenite, Ferrierite, ETS-4 or ETS-10;

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

6. organic-inorganic composite mesoporous structures or layered materials;

7. Organic zeolite, organometallic zeolite or coordination compound zeolite in which metal ion and ligand are three-dimensionally bound;

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

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

10. Metals, metal oxides, and complexes of metals and metal oxides.
The method of claim 17,

Wherein the linking compounds each independently comprises a compound derived from one or two or more organic compounds selected from the group consisting of, a method for producing a substrate-microparticle film composite using a 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), 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 an alkyl, aralkyl or aryl group which is substituted or unsubstituted C 1 -C 1 7 which may comprise 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, 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, Is a coordination compound capable of double bond, triple bond, diene, diyne, 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 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. box.
The method of claim 17,

Injecting the microparticle-containing solution into the vessel containing the microparticle-containing solution and circulating the microparticle-containing solution by an external reservoir for recovering the used microparticle-containing solution. Method for producing a substrate-microparticle film composite to be used.
The method of claim 17,

The temperature of the micro-particle-containing solution is adjusted to 0 ℃ to 100 ℃, a method for producing a substrate-microparticle film composite using a liquid spray.
The method of claim 24,

The temperature of the vessel containing the microparticle-containing solution and the external storage is adjusted to 0 ℃ to 100 ℃, the method of producing a substrate-microparticle film composite using a liquid spray.
The method of claim 17,

And plasma treatment for plasma treatment to remove impurities remaining on the surface of the substrate coated with the fine particles.
The method of claim 17,

Wherein said substrate contains fibers, wallpaper, closet product, blinder, curtain, plastic, or polymer.