KR102099863B1 - A composition of granular aerogel and aerogel sheet having thereof - Google Patents

Abstract

A granular aerogel composition according to the present invention comprises hydrophobic granular aerogel together with hydrophilic adhesive powder such that static electricity generation of the hydrophobic granular aerogel is suppressed, thereby enabling uniform dispersion and applying functionalities such as moisture transmission, waterproof properties, and heat insulating properties. Also, a functional aerogel sheet applied with the granular aerogel composition has the abovementioned properties, thereby being widely used for clothes, sheets for shoes, and beddings requiring properties such as moisture transmission, waterproof properties, and heat insulating properties.

Description

A composition of granular aerogel and aerogel sheet having the same

The present invention relates to a granular airgel composition and a functional airgel sheet comprising the same, and in particular, it includes a hydrophobic airgel together with an adhesive powder having hydrophilicity to help uniform dispersion of the hydrophobic airgel, moisture permeability, waterproofing, heat insulation, etc. It relates to a granular airgel composition capable of having a functional and functional airgel sheet comprising the same.

In general, aerogel (aerogel) is a high specific surface area (≥500 ㎡ / g) material having a porosity of about 90 to 99.9% and a pore size of 1 to 100 ㎚, ultralight, ultra insulating, ultra low dielectric properties . Due to these excellent properties, research on airgel materials, as well as transparent insulation and environmentally friendly high-temperature insulation, ultra-low dielectric thin films for highly integrated devices, catalysts and catalyst carriers, electrodes for supercapacitors or electrode materials for seawater desalination are actively underway. Is becoming.

Silica aerogels can be largely divided into three types: powder, granular, and monolith, of which the most common powder form.

In the case of powder, it is possible to commercialize it in a form such as an airgel blanket or airgel sheet by complexing it with fibers. In addition, in the case of a blanket or sheet manufactured using silica airgel, it has flexibility and can be bent, folded, or cut into any size or shape. Accordingly, it can be applied not only to industrial applications such as insulation panels for liquefied natural gas (LNG) ships, thermal insulation materials for vehicles, thermal insulation materials for electric power generation, but also to household goods such as space suits, jackets, and athletic shoes. In addition, it can be applied to the roof or floor fire doors in houses to prevent fire.

On the other hand, in general, an airgel is prepared by preparing a wet gel from a silica precursor such as water glass or tetraethoxysilane (TEOS), and then removing the liquid component inside the wet gel without breaking the microstructure. At this time, the wet gel is filled with water or alcohol. Accordingly, when the solvent is removed through a drying process, shrinkage and cracking of the pore structure occurs due to high surface tension of water at the gas / liquid interface while the liquid solvent vaporizes in the gas phase.

As a result, a decrease in specific surface area and a change in pore structure occur in the final silica airgel produced. Therefore, in order to maintain the pore structure of the wet gel, it is necessary to replace water or alcohol having a high surface tension with an organic solvent having a relatively low surface tension. In addition, the dried silica airgel maintains a low thermal conductivity immediately after drying, but has a disadvantage in that the thermal conductivity gradually increases as the hydrophilic silanol group (Si-OH) present on the silica surface absorbs water in the air. Therefore, in order to maintain a low thermal conductivity, a silica airgel having a hydrophobically modified silica airgel surface is widely used.

However, in the case of such a hydrophobic silica airgel, since the structural strength is weak and the insulation is high, it has a property of being easily charged. For example, when the silica airgel is refined to a particle size of 100 µm or less, there is a problem that it is difficult to handle by static electricity due to frequent friction between particles due to characteristics of a very small airgel. In addition, there is a problem that the silica airgel has a large amount of powder dropping and the charged powder is transferred to the surroundings.

In order to solve the above problems, a technique of producing an airgel through a process of adding a conductive polymer to an alkali silicate aqueous solution and gelling it and hydrophobizing it has been introduced. However, such a process still has difficulty in maintaining a low thermal conductivity because the hydrophilicity is partially imparted to the particles, and the production cost is greatly increased due to the complicated process.

Republic of Korea Patent Publication No. 10-2017-0072790 (June 27, 2017)

The present invention has been devised to solve the above problems, and includes a hydrophobic airgel together with an adhesive powder having hydrophilicity to help uniform dispersion of the hydrophobic airgel, and granules capable of having moisture permeability, waterproofing, heat insulation, etc. An object of the present invention is to provide a type airgel composition.

Another object of the present invention is to provide a functional airgel sheet that exhibits functions such as moisture permeability, water resistance, heat insulation, and cold feeling as the granular airgel is included.

The present invention relates to a granular airgel composition and a functional airgel sheet comprising the same.

One aspect of the present invention, SiO ₂ , Al ₂ O ₃ , TiO ₂ And ZrO ₂ Granular airgel characterized in that it comprises an airgel containing any one or a plurality of metal oxides and a hydrophilic adhesive in powder form It relates to a composition.

In the present invention, the airgel has an average particle diameter of 1 Μm It is characterized by being 1 to 1 mm and a density of 10 to 200 kg / m 3.

In addition, the hydrophilic adhesive has an average particle diameter of 1 to 500 μm, a density of 0.1 to 5 g / cm 3, and a melt index at 150 ° C. and 2.16 kg of 1 to 30 g / 10min.

The granular form in the present invention The airgel composition is characterized in that the airgel and the adhesive are mixed in a weight ratio of 7.5 to 9.5: 0.5 to 2.5.

In addition, the granular airgel composition further includes any one or a plurality of phase change materials selected from hydrated inorganic salts, dimethylpropanediol, hexamethylpropanediol, polyethylene glycol, polytetramethyl glycol and polyethylene terephthalate-polyethylene glycol copolymer. It is characterized by.

Other aspects of the invention are sheet and granular Functional airgel sheet comprising an airgel composition, the sheet is a functional airgel sheet, characterized in that the granular airgel composition is heat-pressed on one or both sides of the base layer and the base layer comprising one or a plurality of sheet layers It is about.

At this time, the sheet includes any one or a plurality of selected from woven fabric, knit, non-woven fabric, film, natural leather and artificial leather, when the sheet is made of a constriction of fibers. The fiber included in the sheet is characterized in that it is a fiber having a release cross-section.

In addition, the sheet is characterized in that it further comprises a polytetrafluoroethylene film.

The granular airgel composition according to the present invention includes a hydrophobic airgel together with an adhesive powder having a hydrophilic property, thereby helping to uniformly disperse the static airgel by inhibiting the generation of static electricity, and imparting moisture permeability, waterproofing, heat insulation, etc. .

In addition, the functional airgel sheet to which the granular airgel composition is imparted can be widely used in garments, footwear sheets, bedding, etc., which require properties such as moisture permeability, waterproofness, and heat insulation as they have the above characteristics.

1 is a schematic cross-sectional view of a nonwoven fabric produced by the method for manufacturing a nonwoven fabric according to the present invention.
Figure 2 shows a schematic process diagram of a non-woven fabric manufacturing method according to an embodiment of the present invention.
Figure 3 shows a schematic process diagram of a non-woven fabric manufacturing method according to an embodiment of the present invention.
4 and 5 show a schematic process diagram of a non-woven fabric manufacturing method according to an embodiment of the present invention.
6 to 9 are schematic cross-sectional views of a nonwoven fabric having a PTFE film, a dot adhesive layer, and a filler layer according to an embodiment of the present invention.

Hereinafter, for example and comparative example, granules according to the present invention The airgel composition and functional airgel sheet comprising the same will be described in more detail. The following specific examples are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art.

Therefore, the present invention is not limited to the specific examples presented below, but may be embodied in other forms, and the specific examples presented below are only described to clarify the spirit of the present invention, and the present invention is not limited thereto.

At this time, unless there are other definitions in the technical terms and scientific terms to be used, it means that those skilled in the art to which the present invention pertains have the meanings commonly understood, and unnecessarily obscure the subject matter of the present invention in the following description. Descriptions of possible known functions and configurations are omitted.

Also, the singular form used in the specification and the appended claims may be intended to include the plural form unless otherwise indicated in the context.

In the present invention, the granular airgel composition is characterized by comprising an airgel containing a plurality of metal oxides and a hydrophilic adhesive in powder form.

In the present invention, the airgel is a porous material having hydrophobicity on the surface, and may be composed of various materials such as inorganic, organic or organic-inorganic hybrids. The airgel includes a nanostructure in which a plurality of pores and microfine particles surrounding these pores are connected to each other. The inside of the pore may be vacuumed or filled with any gas such as oxygen, helium, nitrogen, or carbon, depending on the application or method of the material.

Inorganic airgels include silica (SiO ₂ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), alumina (Al ₂ O ₃ ), hafnia (HfO ₂ ), yttria , Y ₂ O ₃ ), ceria (CeO ₂ ), or a combination of metal oxides independently selected from the combination thereof, but are not limited thereto.

Organic airgels are generally formed from carbon-based polymer precursors. Such polymer materials include lesocinol formaldehyde, polyimide, polyacrylate, polymethyl methacrylate, acrylate oligomer, polyoxyalkylene, polyurethane, polyphenol, polybutadiene, trialkoxysilyl terminated polydimethylsiloxane, Polystyrene, polyacrylonitrile, polyfurfural, melamine-formaldehyde, cresol formaldehyde, phenolfurfural, polyether, polyol, polyisocyanate, polyhydroxybenz, polyvinyl alcohol dialdehyde, polycyanurate, polyacrylamide , Various epoxy, agar, agarose, chitosan and combinations thereof. As an example, organic RF airgels can typically be formed by sol-gel polymerization of formaldehyde with lesocinol or melamine under alkaline conditions.

Examples of the organic-inorganic hybrid airgel include, but are not limited to, silica-PMMA, silica-chitosan, or a composite of the aforementioned organic airgel and inorganic airgel.

The airgel of the present invention is more specifically any one selected from silica, alumina, titania, and zirconia, and among these, silica is preferable because it can increase productivity while maintaining low thermal conductivity.

The size of the particles of the airgel can be reduced or classified to a desired size by a jet mill or other method of reducing the size, and is not particularly limited. Usually, the granular airgel has an average particle size. It is preferably 1 µm to 1 mm.

In addition, the airgel according to the present invention may have a density of 10 to 200kg / ㎥. Due to the high porosity in the above range, it shows a low thermal conductivity, and at the same time, a sheet of low weight can be produced.

In the present invention, the airgel is not limited to a manufacturing method. As an example, as shown in Korean Patent Publication No. 10-2017-0132829, a sol containing colloidal particles is reacted with a silicon oxide containing hydrogen-substituted or unsubstituted organic radicals, and a gel is formed therefrom to impart hydrophobicity to the particles. can do. In this case, the pores are filled with liquid, have a very low density, can control the carbon content to a certain range or less, and can exhibit a very large BET surface area of more than 300 m 2 / g.

In the present invention, the hydrophilic adhesive is mixed with the airgel in a powder form, and has hydrophilicity in itself, thereby suppressing the generation of static electricity of the hydrophobic airgel and increasing miscibility so that it can be more uniformly dispersed.

In addition, the hydrophilic adhesive has a thermoplastic (thermoplastic) is applied to the base layer together with the airgel, and when heated, the adhesive particles may melt to bond the base layer and the airgel. At this time, according to the size and mixing amount of the adhesive particles, the contact area between the airgel and the adhesive can be adjusted, and through this, various characteristics such as adiabatic, adsorption, and cold feeling of the airgel can be more actively exhibited.

In the present invention, the hydrophilic adhesive is not limited to the type of the composition in the form of a polymer that can be produced in powder form with thermoplasticity, and is preferably a thermoplastic polyurethane (TPU).

In the present invention, the TPU can be obtained by reacting a bifunctional isocyanate composition with one or more bifunctional polyhydroxy compounds.

The bifunctional isocyanate composition may be any one or a plurality of aromatic isocyanates, aliphatic isocyanates and alicyclic isocyanates, more preferably diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane di And isocyanate, isophorone diisocyanate, and naphthalene diisocyanate.

The bifunctional polyhydroxy compound has a weight average molecular weight of about 500 to about 20,000, and the compound includes diols such as polyesteramide, polythioether, polycarbonate, polyacetal, polyolefin, polysiloxane, polybutadiene, and the like. Can be selected from polyesters and polyethers and mixtures thereof. Other dihydroxy compounds, such as known styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene-butadiene-styrene (SEBS), or styrene-isoprene-butadiene-styrene (SIBS) blocks Hydroxy terminated styrene block copolymers such as copolymers can also be used.

Particularly useful bifunctional polyhydroxy compounds are the products obtained by polymerization of cyclic oxides, for example ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran, in the presence of a bifunctional initiator in the polyether diol, if necessary. This is included. Suitable initiator compounds contain two active hydrogen atoms, including water; Butanediol; Ethylene glycol; Propylene glycol; Diethylene glycol; Triethylene glycol; Dipropylene glycol; 1,3-propane diol; Neopentyl glycol; 1,4-butanediol; 1,5-pentanediol; 1,6-pentanediol; Etc. are included. Mixtures of initiators or cyclic oxides can be used here.

Particularly useful polyether diols include polyoxypropylene diols and poly (oxyethylene-oxypropylene) diols obtained by simultaneous or continuous addition of ethylene or propylene oxide to a bifunctional initiator. A random copolymer having an oxyethylene content of about 10 to 80% by weight based on the total weight of the oxyalkylene unit, a block copolymer having an oxyethylene content of about 25% by weight or less and an oxyethylene content of about 50% by weight or less Random / block copolymers having a can be mentioned, in particular copolymers having at least some oxyethylene groups at the ends of the polymer chain. Other useful polyether diols include polytetramethylene diols obtained by polymerization of tetrahydrofuran. Polyether diols containing low levels of unsaturation (i.e., less than about 0.1 milliequivalents per gram of diol) are suitable.

Other diols include dispersions or solutions of addition or condensation polymers in diols of the type described above. Such modified diols, sometimes also referred to as “polymeric diols,” are obtained by in situ polymerization of one or more vinyl monomers, such as styrene and acrylonitrile, in polymeric diols, such as polyether diols, or in polymeric diols. Products obtained by in situ reaction of polyisocyanates with amino- and / or hydroxyfunctional compounds such as triethanolamine are included.

Polyester diols that can be used include dihydric alcohols such as ethylene glycol; Propylene glycol; Diethylene glycol; 1,4-butanediol; Neopentyl glycol; 2-methylpropanediol; 3-methylpentane-1,5-diol; 1,6-hexanediol; Cyclohexane dimethanol; And mixtures of such dihydric alcohols with divalent carboxylic acids or ester-forming derivatives thereof (eg, succinic acid, glutaric acid and adipic acid, or dimethyl esters thereof, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride, Dimethyl terephthalate and mixtures thereof) hydroxyl-terminated reaction products.

Polycarbonate diols that can be used include glycols such as diethylene glycol, triethylene glycol, or those produced by reacting hexanediol with formaldehyde. Suitable polyacetals can also be prepared by polymerization of cyclic acetals.

Here, as the chain weight agent, an aliphatic diol, such as ethylene glycol; 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,2-propanediol; 2-methylpropanediol; 1,3-butanediol; 2,3-butanediol; 1,3-pentanediol; 1,2-hexanediol; 3-methylpentane-1,5-diol; Diethylene glycol; Dipropylene glycol; And tripropylene glycol, and amino alcohols such as ethanolamine, N-methyldiethanolamine, and the like, of which 1,4-butanediol is preferred.

The hydrophilic adhesive according to the present invention preferably has a melt index of 1 to 30 g / 10min, more preferably 10 to 25 g / 10min, measured according to ASTM D1238 at 150 ° C. and 2.16 kg. When the melt index is less than the above range, the fluidity of the adhesive may be excessively increased to increase the amount of the hydrophilic adhesive coated on the airgel, and when the melt index exceeds the above range, the adhesive area between the adhesive and the base layer or the adhesive and the airgel By reducing this, the airgel can easily escape from the base layer.

In addition, the hydrophilic adhesive preferably has an average particle diameter of 1 to 3 mm and a density of 0.1 to 5 g / cm 3. In the above range, in particular, uniform mixing with the airgel can be achieved at the average particle diameter, and it is preferable because the coating area and the coating amount of the hydrophilic adhesive coated on the airgel during melting can be appropriately adjusted.

In the granular airgel composition according to the present invention, it is preferable that the airgel and the adhesive are mixed in a weight ratio of 7.5 to 9.5: 0.5 to 2.5. If it has a composition ratio outside the above range, the adhesive layer covers the microporous surface of the airgel surface or the substrate layer due to the excessive amount of the adhesive component, so that characteristics such as moisture permeability, water resistance, cold feeling, etc. are difficult to develop or the airgel can easily escape even with weak friction. .

Granular according to the invention The airgel composition may further include various additives to improve physical properties of the composition in addition to the above components. These additives may include, for example, internal lubricants, fluidizing agents, heat stabilizers, light stabilizers, pigments, antioxidants, plasticizers, fillers, and the like, and those skilled in the art may use the additives without detracting from the purpose of the present invention. It can be added freely. For example, when the fluidity of the hydrophilic adhesive is low and air is trapped on the surface of the adhesive and the airgel or the adhesive and the substrate layer, a plasticizer that reduces the porosity of the adhesive may be included.

The granular airgel composition according to the present invention may further include a phase change material (PCM). The phase change material may be added for temperature control of the sheet containing the granular airgel composition.

When people are doing activities such as travel, work, conversation, and exercise, the clothes they wear can get wet or uncomfortable as they get hot. PCM has a function of storing heat and controlling temperature by alleviating radiation emitted from the sun in the microenvironment of the wearer or simply absorbing energy generated by the body. When the outside temperature rises, the PCM “borrows” the energy of a warm body or rising ambient temperature, changing it from a static temperature to a fluid temperature.

PCM is a material with high heat of fusion, which melts or hardens at a certain temperature and can store or release large amounts of energy. Generally, it is a material that absorbs and stores 3 to 12 ° C when it is 25 to 35 ° C, and then dissipates heat when the ambient temperature is below 22 to 23 ° C to protect the base material and release stored heat at subzero temperatures.

Examples of such PCM include hydrated inorganic salts such as hydrated calcium chloride, lithium nitrogen oxide, and manganese (Na ₂ SO ₄ ); Polyhydric alcohols such as DMP (Dimethyl Propanediol) and HMP (Hexamethyl Propanediol); And polytetramethyl glycol and polyethylene terephthalate-polyethylene glycol. In addition, linear chain alkanes (C _n H _{2n + 2} ), octatecane (C ₁₈ H ₂₈ ), heptadecane (C ₁₇ H ₃₆₎ ), ZrC, Caprylic acid (CH ₃ (CH ₂ ) ₆ COOH), Glauber's salt, Manganese nitrate hexahydrate, Mn (NO ₃ ) ₂ H ₂ O), nitrification Manganese nitrate hexahydrate, Mn (NO ₃ ) ₂ H ₂ O), zinc nitrate hexahydrate, Zn ₂ (NO ₃ ) ₂ 6H ₂ O, etc. may be further included.

Since the PCM is changed from a solid to a liquid and a liquid to a solid according to temperature, it is preferable to be filled with a porous medium or capsule. At this time, examples of the porous medium may include activated carbon or silica as described above, and it is preferable that the capsule uses a material capable of emulsion polymerization such as paraffin.

The PCM does not limit the particle size, but preferably has a particle size similar to that of the airgel and adhesive, and specifically, 1 μm to It is good to have a size of 1 mm.

The PCM does not limit the amount of addition, it is good to add 10 to 30 parts by weight compared to 100 parts by weight of the granular airgel composition. When adding less than 10 parts by weight, the insulating properties of the sheet are not properly expressed, and when it is added more than 30 parts by weight, the adhesive strength may drop significantly due to an increase in the adhesive target of the adhesive.

In addition, the composition may further include one or a plurality of metal nanoparticles to prevent static electricity and impart antimicrobial properties independently of PCM.

The metal nanoparticles are nanoparticles having a length of several to hundreds of nanometers in at least one direction, and have a charge on the surface, thereby being hydrophilic, and can compensate for the insufficient hydrophilicity of the airgel. In addition, as described above, the charge on the surface destroys the cell membrane of bacteria and has antibacterial properties. In particular, gold (Au) is weakly acidic and strongly binds to weak bases such as thiols and amines, and proteins with cysteine and lysine residues bind gold nanoparticles to change their biological function.

Examples of the metal constituting the metal nanoparticles include gold, silver, copper, platinum, palladium, nickel, and iron, and these may be used alone or in a mixed composition of two or more.

The metal nanoparticles are not limited in shape. For example, it may be sphere, rod, pyramid, star-shaped, and core-shell, even when two or more different shapes are mixed. It is okay.

The metal nanoparticles may further bind one or more hydrophilic polymers to the surface to further increase the hydrophilicity of the surface. At this time, as an example of the hydrophilic polymer, polyalkylene glycol (poly (alkylene glycol)) is polyethylene glycol (PEG); Methoxy polyethylene glycol (MPEG); Methoxy polypropylene glycol; Copolymers of polyethylene glycol and methoxypolypropylene glycol; Polyethylene glycol-diacid; Polyethylene glycol monoamine; Methoxypolyethylene glycol monoamine; Methoxy polyethylene glycol hydrazide; Methoxypolyethylene glycol imidazole; Or it may be a copolymer of two or more of polyethylene glycol, methoxy polypropylene glycol, polyethylene glycol-diacid, polyethylene glycol monoamine, methoxypolyethylene glycol monoamine, methoxypolyethylene glycol hydrazide and methoxypolyethylene glycol imidazole.

The metal nanoparticles do not limit the particle size, but it is preferable to have a particle size similar to or smaller than that of the airgel and adhesive, and in detail, it is preferable to have a size of 1 nm to 1 mm.

The amount of the metal nanoparticles is not limited, and for example, the metal nanoparticles are preferably added in an amount of 1 to 10 parts by weight compared to 100 parts by weight of the granular airgel composition. When adding less than 1 part by weight, the heat dissipation properties and mechanical properties may be deteriorated due to the decrease in the dispersion properties of the composition, and when it is added more than 10 parts by weight, the moisture adsorption of the composition is remarkable, and the adhesive strength may also drop significantly.

The present invention is granular prepared as described above Functional airgel sheet comprising an airgel composition and a method of manufacturing the same may be included. At this time, the sheet is characterized in that the granular airgel composition is thermocompressed on one or both surfaces of the substrate layer including one or a plurality of sheet layers.

To explain this in more detail through the manufacturing method, Figure 1 is an example of the airgel sheet according to the present invention, the base layer constituting the sheet is a non-woven fabric, more specifically, a non-woven fabric to which the needle punching method is applied, a pair of base layers After forming the airgel layer 200 by laminating the granular airgel composition between (100), the nonwoven fabric is made through a needle punching process.

1. Airgel layer formation step

The step of forming the airgel layer is granular between the pair of fiber layers 10. This is a process for manufacturing synthetic fibers laminated with an airgel composition. Incidentally, in the step of forming the airgel layer, the granular airgel composition is uniformly distributed on the surface of the first fiber layer 10, and the second fiber layer 120 is stacked on top of it, followed by a card machine or an airlay method. The airgel layer 20 formed by the granular airgel composition is made to produce synthetic fibers having a central portion. At this time, the airgel in the form of granules is uniformly applied to the surface of the first fiber layer 10 by the application device 10. If it expands, the first fiber layer 10 is moved in the horizontal direction, and the coating device 10 is in the state in which the airgel of the granular state having the predetermined particles is accommodated, in the upward direction of the first fiber layer 10. Is placed. At this time, the dispensing roller 1 for applying the airgel to the surface of the first fiber layer 10 by rotation is provided on the outlet side of the coating device 10. Accordingly, in the step of forming the airgel layer, the airgel in the form of granules is applied to the surface of the first fiber layer 10 in the process in which the first fiber layer 10 passes through the coating device 10, and thereafter, the first As the fiber layer 10 is laminated on the surface of the first fiber layer 10, the airgel layer 20 is formed.

2. Punching stage

The punching step is a process of manufacturing the nonwoven fabric by supplying the manufactured synthetic fiber to the needle punching device 40. In other words, in the punching step, a plurality of needles are moved up and down from the upper side of the synthetic fiber while the fibers of the first fiber layer 10 and the second fiber layer 120 are randomly combined with each other so that a nonwoven fabric is manufactured. do.

4 and 5, the method of manufacturing a nonwoven fabric according to an embodiment of the present invention is impregnated with a pair of fiber layers 10 in a liquid adhesive for a predetermined time, and then impregnated a pair of fiber layers 10 ) Is compressed, and then the airgel composition is uniformly applied and laminated between the pair of fiber layers 10, and then dried for a predetermined time to produce a nonwoven fabric.

1. Impregnation stage

The impregnation step is a process of impregnating the pair of fiber layers 10 with a liquid adhesive for a predetermined time. In other words, the impregnation step is the first fiber layer 10 and the second fiber layer 120, the first fiber layer 10 and the second fiber layer 120 in the process of passing through the impregnation tank 40 containing a liquid adhesive, respectively ) Is impregnated. At this time, the adhesive is made of acrylic or SBR (Styrene Butadiene Ruber).

2. Crimping step

The pressing step is a process of pressing the impregnated pair of fiber layers 10. In a second step, in the crimping step, a pair of crimping rollers 60 are respectively provided in front of the first fiber layer 10 and the second fiber layer 120 that have passed through the impregnation tank 40, respectively. The fiber layer 10 and the second fiber layer 120 are respectively compressed in the process of passing through the compression roller 60.

3. Airgel supply stage

The airgel supply step is a process of uniformly applying the granular airgel composition to the surface of the compressed first fiber layer 10. Incidentally, in the supply step, the first fiber layer 10 passing through the compression roller 60 is supplied to the coating device 10, and the first fiber layer 10 passes through the coating device 10. In the process, the coating device 10 uniformly applies the granular airgel composition to the surface of the first fiber layer 10 so that airgel is supplied. At this time, the coating device 10 is accommodated in the airgel in the form of granules having a predetermined particle, the received airgel is the first fiber layer by the rotation of the distribution roller (1) provided on the outlet side of the coating device (10) (10) is applied to the surface.

4. Combination stage

The bonding step is a process of manufacturing the nonwoven fabric by laminating the second fiber layer 120 on the surface of the first fiber layer 10 coated with airgel. If it is further expanded, a pair of bonding rollers 70 preheated to a predetermined temperature or more are provided on the front side of the coating device 10, and the first fiber layer 10 is supplied to the bonding roller 70 side. At the same time, as the second fiber layer 120 is supplied above the first fiber layer 10, the first fiber layer 10 and the second fiber layer 120 are pressed by the bonding roller 70 so that a non-woven fabric is manufactured. do.

The non-woven fabric that has passed through the bonding roller 70 can be sufficiently dried by a low-temperature wind in the process of passing through the drying device.

The sheet layer according to the present invention can be used irrespective of the type as long as it is a sheet-like fiber aggregate manufactured by various methods in addition to the above-described method. In addition to the fiber aggregate, a foamed foam sheet produced by foaming a polymer such as polyurethane can also be used. Do.

For example, the sheet may include any one or a plurality selected from woven fabrics, knits, non-woven fabrics, films, natural leathers, and artificial leathers, and the non-woven fabrics may include, besides needle punching, spunbond, spunlace, and meltable. Manufacturing methods such as roll, electrospinning and thermal bonding can be applied. That is, the nonwoven fabric may be manufactured by applying both mechanical, chemical, and complex methods as a bonding method of the web.

When applying the film form to the sheet in the present invention, it is preferable that the film is a porous film. At this time, the size of the pores formed in the film is not limited in the present invention, and can be freely set according to the purpose of use of the sheet. For example, when the sheet is used for clothing or footwear, it is preferable that pores having a size of 1 nm to 10 µm are formed in order to quickly discharge sweat in the form of water vapor generated from the body.

In addition, the sheet layer may further include a polytetrafluoroethylene (PTFE) film in addition to the above types. The polytetrafluoroethylene film is also commonly referred to as Teflon, and is mainly applied to kitchen utensils such as frypens.

The PTFE film (trade name Gore-tex ^ⓡ ) is ^intended to focus on generating countless micro-pores when casting a composition and then stretching it with heating. Moisture as a micro-pore with low reactivity and hydrophobic characteristics peculiar to Teflon resin It can always maintain water repellent and moisture permeable properties as it escapes.

In the present invention, the PTFE film may be located between the first fiber layer and the second fiber layer constituting the sheet layer as shown in Figures 6 and 7. At this time, between the first fiber layer or the second fiber layer and the PTFE film 400, the granular airgel composition 200 or the adhesive layer 300 in the form of a dot may be located, through which the sheet layer and the PTFE film can be firmly bonded. have.

In addition, the sheet containing the PTFE film is laminated on the non-woven fabric layer 100 instead of the granular airgel composition 200 on both sides as shown in Figure 8, and after applying the airgel composition 200 on the surface of the non-woven fabric layer on both sides, it is again a non-woven fabric The structure covered with the layer 100 may be taken, or the filler layer 500 may be further formed on the surface of the nonwoven layer 100 in the sheet structure of FIG. 6 as shown in FIG. 9. At this time, the filler is mainly laminated to increase the thermal insulation effect, and may include a filler that increases thermal insulation such as goose down, duck down, wellon, thinsulate, and the like.

The filler layer may be formed on all of the sheet layers having various structures included in the present invention in addition to the structure of FIG. 9 as described above, and the present invention is not limited thereto.

Functional airgel sheet according to the present invention may have a variety of structures in addition to the above structure. That is, the base layer including one or a plurality of sheet layers and the granular form on one or both sides of the base layer It is only necessary to satisfy the structure in which the airgel composition is applied and thermally compressed. For example, one sheet layer may be thermally compressed by covering one surface with a granular airgel composition, or two or more sheet layers may be stacked, and the granular airgel composition may be positioned between the sheet layer and the sheet layer. .

The functional airgel sheet is not limited to a manufacturing method. As an example, a PTFE film and a nonwoven fabric may be passed through a laminating machine, and thermal compression may be performed by applying the granular airgel composition to a surface where the film or nonwoven fabric is in contact with each other and passing a roller preheated to a predetermined temperature or higher. Through this, a functional airgel sheet to which insulation, moisture permeability, and water resistance are finally provided can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are only examples for explaining the present invention in more detail, and the present invention is not limited by the following examples.

The physical properties of the specimens prepared through the following examples and comparative examples were measured as follows.

(Aeration)

ASTM D 737 method was used to measure the air permeability under the conditions of an area of 38 cm 2 and a pressure of 125 Pa.

(Permeability)

Using a moisture permeability meter (LabThink, PERME (W3 / 0120)), the temperature applied to the film specimen in the sealed chamber is 38 ° C., the relative humidity (RH) of the outer cell is 90%, and the outer cell is 24 hours under N ₂ carrier gas conditions. Moisture permeated through the film from and penetrated into the inner cell was measured.

(Thermal conductivity)

 The prepared specimens were measured using a HC-074 Ekoseiki) thermal conductivity meter.

(Example 1)

First, each blend, but the hydrophobic airgel (Enova ^ⓡ IC3120 Cabot) and hydrophilic adhesives (TPU 8036, JCC Korea) as airgel composition, the hydrophobic airgel with hydrophilic adhesives, respectively 8: was prepared by mixing 2 weight ratio.

Next, two layers of a non-woven fabric (basis weight: 70 g, material: PET, thickness: 2 mm) were prepared as a base layer, and the airgel composition prepared as above was applied between the non-woven fabrics. Then, the base layer coated with the airgel composition was completely compressed by passing through a Thermoplastic Scattering Machine set at 150 ° C to prepare a specimen. The physical properties of the prepared specimens were measured and described in Table 1 below.

(Example 2)

In the preparation of the specimen in Example 1, as the base layer, two nonwoven fabrics and polytetrafluoroethylene having a three-layer structure (average pore size: 2.5 μm, total thickness: 120.3 (1 layer: 80.69 μm, 2 layers: 29.71 μm, 3) Layer: 9.9 µm) The composition of the specimen was sequentially non-woven fabric-aerogel composition-PTFE-aerogel composition-non-woven fabric, except that the specimens were prepared in the same manner. It is described in 1.

(Example 3)

In Example 2, except for the addition of 15 parts by weight of the phase change material capsule containing manganese nitrate hexahydrate as an internal phase change material in the zirconia as an average particle diameter of 0.5 µm in the composition when preparing the specimen. Specimens were prepared in the same way. The physical properties of the prepared specimens were measured and described in Table 1 below.

(Example 4)

In Example 3, when preparing the specimen, the specimen was prepared in the same manner except that 5 parts by weight of gold nanoparticles (GNP) having an average particle diameter of 10 nm was added to 100 parts by weight of the composition. The physical properties of the prepared specimens were measured and described in Table 1 below.

(Example 5)

In Example 1, the composition was prepared by mixing the hydrophobic airgel and the hydrophilic adhesive in a weight ratio of 9: 1, respectively, and the specimens were prepared in the same manner. The physical properties of the prepared specimens were measured and described in Table 1 below.

(Comparative Example 1)

In Example 1, a general adhesive was used instead of the powdery hydrophilic adhesive. Specifically, a hydrophobic airgel was applied to one surface of the nonwoven fabric, and then a polyurethane adhesive (Samsung Chemical, SPU-7835) was applied by a gravure roll coating method, and another nonwoven fabric was laminated and laminated on it to prepare a specimen. The physical properties of the prepared specimens were measured and described in Table 1 below.

(Comparative Example 2)

When preparing the composition in Example 2, a specimen was prepared in the same manner, except that the hydrophobic airgel and the hydrophilic adhesive were each mixed at a weight ratio of 9.8: 0.2. The physical properties of the prepared specimens were measured and described in Table 1 below.

(Comparative Example 3)

When preparing the composition in Example 2, a specimen was prepared in the same manner, except that the hydrophobic airgel and the hydrophilic adhesive were mixed at a weight ratio of 7: 3, respectively. The physical properties of the prepared specimens were measured and described in Table 1 below.

(Comparative Example 4)

When preparing the composition in Example 2, a specimen was prepared in the same manner, except that polyvinyl butyral (Mowital ^ⓡ ) was mixed in the same amount as the hydrophilic adhesive. The physical properties of the prepared specimens were measured and described in Table 1 below.

[Table 1]

The sheet manufactured according to the present invention as shown in Table 1 shows excellent physical properties in terms of air permeability, moisture permeability, and thermal conductivity. Specifically, in Example 2, in which the PTFE film was further added, it was found that the moisture permeability was remarkably lowered while maintaining the air permeability to a certain degree, and in Examples 3 and 4 in which the phase change material and gold nanoparticles were further added, the thermal conductivity was significantly improved. You can.

Separately, Comparative Example 1, in which a general adhesive was coated with a gravure roll, showed that the pores in the nonwoven fabric were blocked by the adhesive, and thus, the air permeability was greatly reduced. It can be seen that the thermal conductivity is not reduced because the mixture is not uniformly mixed, or the hydrophilic adhesive in the form of a powder prevents fine pores of the nonwoven fabric or PTFE film, thereby significantly reducing air permeability and moisture permeability. In addition, even in Comparative Example 4 in which a hydrophobic polyvinyl butyral powder adhesive was used instead of a hydrophilic adhesive, the static electricity of the hydrophobic airgel was not properly controlled, so that the air permeability and moisture permeability fell and the thermal conductivity fell together. .

The present invention has been described with reference to the embodiments shown in the drawings, but these are merely examples, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom.

Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

10: coating device
11: Distribution roller
20: heating device
30: adhesive roller
40: needle punching device
50: impregnation tank
60: crimping roller
70: Combine roller
100: fiber layer (non-woven fabric layer)
110: first fiber layer
120: second fiber layer
200: airgel layer
300: dot type adhesive layer
400: PTFE layer
500: filler layer

Claims (10)

A hydrophobic airgel containing any one or a plurality of metal oxides selected from SiO ₂ , Al ₂ O ₃ , TiO ₂ and ZrO ₂ ;
As an internal substance, Octadecane (C ₁₈ H ₂₈ ), Heptadecane (C ₁₇ H ₃₆ ), ZrC, Caprylic acid (CH ₃ (CH ₂ ) ₆ COOH), Grover's salt ), Manganese nitrate hexahydrate, Mn (NO ₃ ) ₂ H ₂ O), Manganese nitrate hexahydrate, Mn (NO ₃ ) ₂ H ₂ O), Zinc nitrate hexahydrate , Zn ₂ (NO ₃ ) ₂ 6H ₂ O), hydrated inorganic salts, dimethylpropanediol, hexamethylpropanediol, polyethylene glycol, polytetramethylglycol and polyethyleneterephthalate-polyethylene glycol Phase change material comprising zirconia;
Metal nanoparticles having an average particle diameter of 1 nm to 1 mm, and consisting of any one or a plurality of metals selected from gold, silver, copper, platinum, palladium, nickel, and iron; And
A hydrophilic adhesive in powder form having an average particle diameter of 1 to 500 μm, a density of 0.1 to 5 g / cm 3, 150 ° C., and a melt index of 1 to 30 g / 10 min at 2.16 kg;
It includes,
Granular airgel composition, characterized in that the airgel and adhesive are mixed in a weight ratio of 7.5 to 9.5: 0.5 to 2.5.
The method of claim 1
The airgel is a granular airgel composition, characterized in that the average particle diameter is 1㎛ to 1㎜.
According to claim 1,
The airgel is granular, characterized in that the density is 10 to 200㎏ / ㎥. Airgel composition.
delete delete delete Functional airgel sheet comprising a sheet and a granular airgel composition,
The sheet is characterized in that the base layer comprising one or a plurality of sheet layers and the granular airgel composition according to any one of claims 1 to 3 are thermocompressed on one or both sides of the base layer. Functional airgel sheet.
The method of claim 7,
The sheet is a functional airgel sheet, characterized in that it comprises any one or a plurality selected from woven, knitted, non-woven, film, natural leather and artificial leather.
The method of claim 8,
Functional airgel sheet, characterized in that the fiber contained in the sheet is a fiber having a release cross-section.
The method of claim 7,
The sheet is a functional airgel sheet, characterized in that it further comprises a polytetrafluoroethylene film.

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