KR102401919B1 - A composite waterproofing sheet laminated with organic and inorganic hybrid water proofing layer comprising organic and inorganic hybrid hollow nanoparticles and non-woven fabric coated with cutoff film and the waterproofing structure and the waterproofing method using thereof - Google Patents

Abstract

In the present invention, a moisture barrier cut-off film is deposited on the bottom surface of the nonwoven fabric, and an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles is formed on the upper surface of the nonwoven fabric, so that heat shielding and insulation and absorption by the organic-inorganic hybrid hollow nanoparticles are performed. It relates to a composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles capable of blocking heat by kinetic energy conversion of heat and a cut-off film deposition nonwoven fabric are laminated, and a waterproof structure and waterproofing construction method using the same, particularly , It is integrally combined with the mortar layer or the ready-mixed concrete layer poured on the organic-inorganic hybrid waterproofing material layer and blocks heat by thermal insulation and heat insulation and kinetic energy conversion of absorbed heat by the organic-inorganic hybrid hollow nanoparticles, resulting from thermal aging Organic-inorganic hybrid containing organic-inorganic hybrid hollow nanoparticles forming an integrated waterproof structure that prevents the separation of the organic-inorganic hybrid waterproofing material layer and the mortar layer or ready-mixed concrete or the separation of the moisture blocking cut-off film from the concrete substrate It relates to a composite waterproofing sheet in which a waterproofing material layer and a nonwoven fabric deposited with a cut-off film are laminated, and a waterproofing structure and waterproofing construction method using the same.

Description

A composite waterproofing sheet laminated with an organic-inorganic hybrid waterproofing layer containing organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric, and a waterproofing structure and waterproofing construction method using the same and inorganic hybrid hollow nanoparticles and non-woven fabric coated with cutoff film and the waterproofing structure and the waterproofing method using thereof}

The present invention relates to a composite waterproofing sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated, and a waterproof structure and waterproofing construction method using the same, and more specifically, to a moisture barrier on the bottom surface of the nonwoven fabric A cut-off film is deposited, and an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles is formed on the upper surface of the nonwoven fabric, and heat shielding and insulation by the organic-inorganic hybrid hollow nanoparticles and kinetic energy conversion of absorbed heat It relates to a composite waterproofing sheet in which an organic-inorganic hybrid waterproofing layer containing an organic-inorganic hybrid hollow nanoparticle capable of blocking and a cut-off film-deposited nonwoven fabric are laminated, and a waterproofing structure and waterproofing construction method using the same.

In particular, the organic-inorganic hybrid waterproofing material layer is integrally combined with the mortar layer or the ready-mixed concrete layer, and the organic-inorganic hybrid hollow nanoparticles block heat by heat shielding and heat insulation and kinetic energy conversion of absorbed heat by thermal aging. Organic/inorganic hybrid hollow nanoparticles comprising organic-inorganic hybrid hollow nanoparticles forming an integrated waterproof structure that prevents the separation of the organic-inorganic hybrid waterproofing layer and the mortar layer or ready-mixed concrete or the separation of the moisture blocking cut-off film from the concrete substrate It relates to a composite waterproofing sheet in which a hybrid waterproofing material layer and a cut-off film deposition nonwoven fabric are laminated, and a waterproofing structure and waterproofing construction method using the same.

In general, when rainwater seeps into concrete structures such as indoors, rooftops, roofs, and basements of various structures, road surfaces such as bridges and roads, and various fluid storage tanks, some of them penetrate inside and adversely affect the durability of the structure. Therefore, waterproof construction is carried out using various waterproofing materials. The waterproof construction as described above is largely divided into an exposed waterproofing construction method and a non-exposed waterproofing construction method. Construction mainly consists of external waterproofing of underground civil structures such as underpasses and subways.

In particular, in the non-exposure waterproofing construction, there is a method of covering the waterproofing surface with a waterproofing sheet such as paper, felt, or cloth impregnated with asphalt or coal tar pitch, and pouring mortar, ready-mixed concrete, etc. thereon.

Looking at the prior art of waterproofing construction with a waterproof sheet as described above, according to Korea Patent Registration 10-0877980 (registration date January 05, 2009), it flexibly contracts and relaxes in response to the behavior of the substrate, even at low and high temperatures. A butyl rubber layer that maintains a semi-solid state so that the waterproof layer can be maintained, and a strength reinforcing layer made of a glass fiber woven fabric attached to the upper portion of the butyl rubber layer to increase the tensile strength and tear strength of the butyl rubber layer. In the self-adhesive film waterproofing sheet, it is attached to the upper portion of the strength reinforcing layer to form another waterproof layer different from the butyl rubber layer, and includes a waterproof protective layer made of a biaxially stretched nylon film to improve the integrity with the urethane coating waterproofing material. A self-adhesive film waterproof sheet is known.

In addition, according to Korea Patent Registration No. 10-0904517 (registration date: June 17, 2009), it is composed of an upper sheet composed of EVA resin from above, glass fiber, an adhesive laminated film and a lower rubberized asphalt sheet, and the adhesive laminate The film, from the top, consists of a first film layer made of medium-density or low-density polyethylene, a second film layer made of low-density or ultra-low-density polyethylene, a third film layer made of metallocene polyethylene, and a third film layer made of polycarbonate. A waterproof sheet comprising an adhesive laminated film is known, characterized in that it is constructed by laminating 4 film layers and a fifth film layer composed of ethylene ethyl acrylate.

In addition, in Korean Patent No. 10-1532734 (registration date June 24, 2015), a first nonwoven sheet layer formed by coating a nonwoven sheet on the top of the concrete surface, and a PET film or PP film, the first A resin film layer applied on the upper surface of the nonwoven fabric sheet layer, a second nonwoven fabric sheet layer formed by applying a nonwoven fabric sheet on the upper surface of the resin film layer, and an acrylic resin on the upper surface of the second nonwoven fabric sheet layer of 10 to 30 μm An acrylic resin layer formed by coating to a thickness, and a top coating urethane layer formed by applying a top coating urethane paint on the upper portion of the acrylic resin layer, wherein the nonwoven fabric sheet has a unit weight of 400 to 600 g/m2 and an initial thickness It is a heavy-duty nonwoven sheet of 4 to 6 mm, and the nonwoven sheet is needle punched so that the punching thickness is 40 to 60% of the initial thickness, and is heated and rolled so that the final thickness is 80 to 100% of the punching thickness. Processed nonwoven sheet and the other end of the first nonwoven sheet layer and the second nonwoven sheet layer positioned on one side and one end of the first nonwoven fabric sheet layer and the second nonwoven sheet layer positioned on the other side are spaced apart from each other. , passing through the spaced area, the lower surface of one side is in contact with the upper surface of the other side of the second nonwoven sheet layer located on one side, and the upper surface of the other side is applied so as to be in contact with the lower surface of one side of the first nonwoven sheet layer located on the other side Passing through the lower fiberglass sheet and the separation region, the lower surface of one side is in contact with the upper surface of one side of the lower fiberglass sheet, and the lower surface of the other side is applied so as to be in contact with the upper surface of one side of the second nonwoven sheet layer located on the other side A waterproof layer comprising a nonwoven fabric sheet is known, comprising a seam portion having an upper fiberglass sheet and a sealant layer applied to an area including an upper region and a spaced region of the nonwoven sheet layer comprising the fiberglass sheet. have.

In addition, in Korean Patent Registration No. 10-1684235 (registration date November 30, 2016), a lower sheet 111 that is a nonwoven fabric, a soft film 112 attached to the upper surface of the lower sheet 111, and the soft film ( The lamination part 110 including the upper sheet 113 which is a nonwoven fabric attached to the upper surface of the 112, and the gas vent part 115 which is a part extending to one side of the lamination part 110 from the upper sheet 113 ) as a waterproofing method using a thermal insulation composite waterproofing sheet capable of discharging moisture by interposing a soft film between the nonwoven fabrics, characterized in that it comprises And, after the bottom surface cleaning step (S1), the primer 220 is applied to the bottom surface 213, after the primer application step (S2) and the primer application step (S2), the primer 220 ), drying step (S3), and after the drying step (S3), while applying the primary waterproofing paint 230 to the bottom surface 213, the insulation composite waterproof sheet 100 is applied to the 1 After the first waterproof paint application and insulation composite waterproof sheet attachment step (S4) and the first waterproof paint application and insulation composite waterproof sheet attachment step (S4) to be attached to the car waterproof paint 230, the insulation composite waterproofing After the secondary waterproof paint application step (S5) of applying the secondary waterproof paint 240 to the upper surface of the sheet 100, and the second waterproof paint application step (S5), the secondary waterproof paint 240 and A drying step (S6) of drying the first waterproof paint 230, and a top coating step (S7) of applying a coating material 250 to the upper surface of the secondary waterproof paint 240 after the drying step (S6) (S7) And, after the top coating step (S7), a drying step (S8) of drying the coating material 250 is included, and the first waterproof paint application and the heat insulation composite waterproof sheet attachment step (S4) is, On the upper surface of the gas vent part 115 of the composite waterproof sheet 100, the lamination part 110 of the heat insulation composite waterproof sheet 100 on the opposite side is laminated, and the lamination part 110 is the gas vent part 115. to cover part of A waterproofing method using a thermal insulation composite waterproofing sheet capable of discharging moisture by interposing a soft film between the nonwoven fabrics is known.

In addition, Korean Patent No. 10-1928412 (registration date December 06, 2018) discloses a roll-type nonwoven fabric 32 having a predetermined thickness; and a gel-type coating film impregnated in the nonwoven fabric 32 and exposed to the surface ( 34); The gel-type coating material 34 is impregnated and packaged in a roll form without attaching a release paper or a release film to the surface of the nonwoven fabric 32 exposed to the surface, and the coating film 34 is a polybutene resin ), mineral oil, polyethylene wax, microcrystalline wax and SEBS-type rubber (Styrene-ethylene-butylene-strene rubber), characterized in that it is composed of a gel This impregnated waterproof sheet is known.

In addition, PET sheet in Korean Patent No. 10-2040813 (registration date October 30, 2019); a solvent-free type adhesive that is applied and attached to one surface of the PET sheet to impart magnetic adhesion; and a release paper attached to one surface of the PET sheet to which the adhesive is applied and attached, wherein the solvent-free adhesive is a thermoplastic resinous elastic rubber, rubber adhesive dough, and adhesion to the soluble subject oil heated in a heating liquid stirrer. The agent is mixed and dissolved, and at least one of a heat stabilizer, an anti-aging agent, a reinforcing agent, and a filler is mixed and manufactured, and the rubber adhesive dough is at least one of natural rubber, SBR rubber, butyl rubber, CR rubber, NBR rubber, and IR rubber. The above and the tackifier are mixed and stirred in a stirrer, and at least one of an active agent, a softener, an anti-aging agent, a reinforcing coagulant, and a filler is added and stirred and mixed, and the above-mentioned solvent-free type of a heating liquid stirrer for producing the adhesive The temperature is 150 ~ 180 ℃, the temperature of the stirrer for producing the rubber adhesive dough is known as a composite waterproof sheet using a PET sheet, characterized in that 50 ~ 90 ℃.

However, the waterproof sheets of the prior art are based on films and/or non-woven fabrics such as PET and PP as a sheet material and have tensile strength, tear strength and high elongation, and have excellent water resistance and durability, but mortar on the upper portion of the waterproof sheet In the case of non-exposure waterproofing construction by pouring ready-mixed concrete, etc., the mortar, ready-mixed concrete, or the upper finishing coating material is not laminated and bonded integrally with the mortar, ready-mixed concrete, or the upper finished coating material, so that the mortar, ready-mixed concrete or the upper finished coating material is lifted or separated from the waterproof sheet and the waterproof performance is lowered There was a problem being

In addition, the waterproof sheet or coating film waterproofing materials of the prior art are rapidly deteriorated in durability, weather resistance, water resistance, and abrasion resistance due to accelerated deterioration due to solar heat absorption and pollution (soot, fine dust, yellow sand, etc.) With this shift, the waterproof sheet or coating film rises easily and cracks occur frequently due to temperature changes caused by rain, snow, etc.

In order to solve this problem, an insulating or heat-shielding waterproofing material has been developed. For example, in Korean Patent No. 10-1936730 (registration date January 03, 2019), the intermediate layer and the top coating layer are sequentially laminated on the surface to be coated, such as asphalt shingle. In the insulation, heat-shielding, and waterproofing coating composition of an asphalt shingle roof that insulates, heat-shields, and waterproofs the roof; In the paint composition, the top coat forming the top coat layer comprises 35-45 wt% of a urethane resin, 5-10 wt% of coal tar, 8-16 wt% of titanium dioxide, and 12-20 wt% of calcium carbonate With 2-4% by weight of cetose, 0.5-3% by weight of polyethylene glycol phenyl ether, 0.5-3% by weight of silicone, 0.5-1.0% by weight of zinc oxide, and 1-4% by weight of sorbitan oleate; An insulating, heat-insulating waterproofing paint composition for an asphalt shingle roof, characterized in that it is composed of 1-5% by weight of white carbon, 15-20% by weight of aluminum silicate micro-hollow body, and the remaining water, has been developed.

At this time, the aluminum silicate (Alumino Silicate) micro hollow body used in the Korea Patent No. 10-1936730 is an ultra-fine ceramic circular hollow body (Ceramic Microsopic Hollow Spheres) powder containing aluminum silicate as a main component, and in the United States It refers to the developed insulator. It is a thermal insulation material or heat shielding material that has heat reflection and heat resistance of the closed air layer of a microscopic hollow sphere with a size of 30 to 100 microns (mm).

However, since the hollow ceramic particles including the aluminum silicate micro-hollow body simply reflect or insulate the sun's heat by the closed air layer, the reflected and insulated heat is absorbed by the waterproofing material and radiant heat is generated to completely dissipate the heat. It could not be blocked or destroyed, so there was a problem that the material swells due to heat aging, which causes deformation and shortens the lifespan.

[Patent Document 001] Korean Patent Registration 10-0877980 (Registration Date January 05, 2009) [Patent Document 002] Korean Patent 10-0904517 (Registration Date: June 17, 2009) [Patent Document 003] Korean Patent Registration 10-1532734 (Registration Date June 24, 2015) [Patent Document 004] Korean Patent 10-1684235 (Registration Date: November 30, 2016) [Patent Document 005] Korean Patent Registration 10-1928412 (Registration Date: December 06, 2018) [Patent Document 006] Korean Patent Registration 10-2040813 (Registration Date: October 30, 2019) [Patent Document 007] Korea Registered Patent 10-1936730 (Registration Date January 03, 2019)

In order to solve the conventional problems, a moisture barrier cut-off film is deposited on the bottom surface of the nonwoven fabric, and an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles is formed on the top surface of the nonwoven fabric, so that the organic-inorganic hybrid hollow nano-particles are formed. A composite waterproofing sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles capable of blocking heat by heat shielding and insulation by particles and kinetic energy conversion of absorbed heat and a cut-off film deposition nonwoven fabric are laminated, and a waterproof structure using the same And to provide a waterproof construction method as a task to be solved.

In particular, the organic-inorganic hybrid waterproofing material layer is integrally combined with the mortar layer or the ready-mixed concrete layer, and the organic-inorganic hybrid hollow nanoparticles block heat by heat shielding and heat insulation and kinetic energy conversion of absorbed heat by thermal aging. The organic/inorganic hybrid waterproofing material layer and the organic/inorganic hybrid hollow nanoparticles forming an integrated waterproof structure that prevents the separation of the mortar layer or the ready-mixed concrete layer or the separation of the moisture barrier cut-off film from the concrete substrate. It is a task to solve the problem of providing a composite waterproof sheet in which a hybrid waterproof material layer and a cut-off film deposition nonwoven fabric are laminated, and a waterproof structure and waterproof construction method using the same.

In order to solve the above problems, a moisture barrier cut-off film is deposited on the bottom surface of the nonwoven fabric, and an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles is formed on the upper surface of the nonwoven fabric, and the organic-inorganic hybrid hollow nanoparticles are A composite waterproofing sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles that can block heat by heat shielding and insulation and kinetic energy conversion of absorbed heat and a cut-off film deposition nonwoven fabric are laminated is a means of solving the problem .

The organic-inorganic hybrid hollow nanoparticles include a hollow core portion; and a shell part surrounding the core part and formed of a plurality of coating layers, wherein the shell part is provided adjacent to the core part and is formed on the first coating layer and a first coating layer for converting thermal energy absorbed from the outside into kinetic energy. However, it is configured to include a second coating layer located at the outermost part to block heat by heat shielding and thermal insulation by the hollow core part and kinetic energy conversion of heat absorbed by the first coating layer as a means of solving the problem do.

The first coating layer of the organic-inorganic hybrid hollow nanoparticles is at least one selected from the group consisting of polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyester, polyacrylate and polyamide as a means of solving the problem.

The second coating layer is at least one selected from the group consisting of silica, quartz, silicon, gold, platinum, silver, copper, cobalt, iron, nickel, manganese, zinc, molybdenum, chromium, and oxides thereof. do it with

The size of the organic-inorganic hybrid hollow nanoparticles is 200 to 300 nm, and the thickness of the first coating layer is 1 to 50 nm as a means of solving the problem.

The organic-inorganic hybrid waterproofing material layer includes 60 to 80 parts by weight of ethylene vinyl acetate (EVA); 5 to 15 parts by weight of a hydration adhesive binder comprising methyl methacrylate monomer (MMA), 2-ethylhexyl acrylate monomer (2-EHAM), and methacrylic acid (MAAC); No. 7 silica sand 90-110 parts by weight; 10 to 20 parts by weight of ordinary cement; 10 to 20 parts by weight of the organic-inorganic hybrid hollow nanoparticles; An appropriate amount of water; the waterproofing composition comprising the composition is applied and thermocompression cured to form a solution to the problem.

The hydration adhesive binder is 860 parts by weight of water, 388 parts by weight of methyl methacrylate monomer (MMA), 526 parts by weight of 2-ethylhexyl acrylate monomer (2-EHAM), and 36 parts by weight of methacrylic acid (MAAC) and 17.4 parts by weight of a 30% aqueous hydrochloric acid solution, 10 parts by weight of a reactive emulsifier represented by the following [Formula 1], and 2.6 parts by weight of ammonium persulfate (APS) as a radical polymerization initiator and sodium metabisulfite (Sodium metabisulfite; A composition comprising 2.5 parts by weight of SMBS, 0.6 parts by weight of sodium bicarbonate as an alkalizing agent and 0.4 parts by weight of tert-butyl hydroperoxide (t-BHP) as a polymerization accelerator is radically polymerized. Let it be a polymerization composition as a means to solve the problem.

[Formula 1]

(Wherein, R is an alkyl group, and X is -SO ₃ NH ₄ or -SO ₃ Na)

A mortar layer or a ready-mixed concrete layer is poured on the organic-inorganic hybrid waterproofing layer, so that the organic-inorganic hybrid waterproofing layer is integrally combined with the mortar or ready-mixed concrete layer, and the lower part of the moisture-blocking cut-off film is in contact with the concrete substrate to form a waterproof structure. as a means of solving the problem.

After the hydration adhesive binder is cured by coating the No. 7 silica sand and ordinary cement particles, the No. 7 silica sand is hydrated by alkali and water of the mortar layer or the ready-mixed concrete layer poured on the organic-inorganic hybrid waterproofing material layer, and the coating is peeled off. And by exposing the ordinary cement particles to be integrally combined with the mortar layer or the ready-mixed concrete layer, the organic-inorganic hybrid waterproofing material layer and the mortar layer or the ready-mixed concrete layer are not separated from each other as a means of solving the problem.

The organic-inorganic hybrid waterproofing material layer blocks heat by heat shielding and thermal insulation by the hollow core part of the organic-inorganic hybrid hollow nanoparticles and kinetic energy conversion of the heat absorbed by the first coating layer, resulting from thermal aging To prevent the separation of the organic-inorganic hybrid waterproofing layer and the mortar layer or the ready-mixed concrete layer or the separation of the moisture barrier cut-off film from the concrete substrate is a means of solving the problem.

It is a means of solving the problem that a nonwoven fabric is further laminated on the lower surface of the moisture barrier cut-off film layer.

A polyurethane layer is further formed on the lower surface of the moisture barrier cut-off film layer as a means of solving the problem.

The moisture barrier cut-off film layer is selected from a hot melt polyester film, a hot melt polyethylene film, a hot melt polypropylene film or a hot melt polyurethane film to be thermally deposited on the nonwoven fabric as a means of solving the problem.

In addition, the present invention comprises the steps of pre-treating the concrete substrate to be waterproofed; attaching a composite waterproofing sheet in which an organic-inorganic hybrid waterproofing material layer containing the organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated to the pretreated concrete substrate; A waterproof construction method using a composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated, including the step of pouring mortar or ready-mixed concrete on the composite waterproof sheet do it as a solution.

After the step of pre-treating the concrete substrate, in order to reinforce the adhesion of the bottom surface of the composite waterproof sheet in which the concrete substrate and the organic-inorganic hybrid waterproofing layer containing the organic-inorganic hybrid hollow nanoparticles and the cut-off film deposition nonwoven fabric are laminated, the pre-treated A means of solving the problem is to include the step of applying a self-leveling agent, an adhesive primer, or a polyurethane paint to the concrete substrate.

The composite waterproof sheet in which the organic-inorganic hybrid waterproofing material layer and the cut-off film deposition nonwoven fabric are laminated and the waterproof structure and waterproof construction method using the same of the present invention include a moisture barrier cut-off film is deposited on the bottom of the nonwoven fabric, and the An organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles is formed on the upper surface of the nonwoven fabric, so that heat shielding and insulation by the organic-inorganic hybrid hollow nanoparticles and heat can be blocked by kinetic energy conversion of absorbed heat.

In particular, the organic-inorganic hybrid waterproofing material layer is integrally combined with the mortar layer or the ready-mixed concrete layer, and the organic-inorganic hybrid hollow nanoparticles block heat by heat shielding and heat insulation and kinetic energy conversion of absorbed heat by thermal aging. There is an excellent effect of forming an integrated waterproof structure that prevents the separation of the organic-inorganic hybrid waterproofing layer and the mortar layer or the ready-mixed concrete layer or the separation of the moisture blocking cut-off film from the concrete substrate.

1 is a perspective view of a composite waterproof sheet according to an embodiment of the present invention;
Figure 2 is a cross-sectional view of the organic-inorganic hybrid hollow nanoparticles according to an embodiment of the present invention;
3 is an organic-inorganic hybrid hollow nanoparticle manufacturing process diagram of the present invention
Figure 4 is a manufacturing process apparatus diagram of the composite waterproof sheet of the present invention
5 is an electron microscope image of the organic-inorganic hybrid hollow nanoparticles of the present invention;
6 is an electron microscope image of the organic-inorganic hybrid hollow nanoparticles of the present invention;
7 is an electron microscope image of the organic-inorganic hybrid hollow nanoparticles of the present invention;
8 is an electron microscope image of the organic-inorganic hybrid hollow nanoparticles of the present invention;

In the present invention, a moisture barrier cut-off film is deposited on the bottom surface of the nonwoven fabric, and an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles is formed on the upper surface of the nonwoven fabric, so that heat shielding, insulation and absorption by the organic-inorganic hybrid hollow nanoparticles It features a composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles that can block heat by converting the kinetic energy of the generated heat and a cut-off film-deposited nonwoven fabric are laminated.

The organic-inorganic hybrid hollow nanoparticles include a hollow core portion; and a shell part surrounding the core part and formed of a plurality of coating layers, wherein the shell part is provided adjacent to the core part and is formed on the first coating layer and a first coating layer for converting thermal energy absorbed from the outside into kinetic energy. However, it is configured to include a second coating layer located in the outermost part, and as a feature of the technical configuration, it blocks heat by heat shielding and thermal insulation by the hollow core part and kinetic energy conversion of heat absorbed by the first coating layer. do.

The first coating layer of the organic-inorganic hybrid hollow nanoparticles is at least one selected from the group consisting of polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyester, polyacrylate and polyamide.

The second coating layer is at least one selected from the group consisting of silica, quartz, silicon, gold, platinum, silver, copper, cobalt, iron, nickel, manganese, zinc, molybdenum, chromium, and oxides thereof. do it with

The size of the organic-inorganic hybrid hollow nanoparticles is 200-300 nm, and the thickness of the first coating layer is 1-50 nm.

The organic-inorganic hybrid waterproofing material layer includes 60 to 80 parts by weight of ethylene vinyl acetate (EVA); 5 to 15 parts by weight of a hydration adhesive binder comprising methyl methacrylate monomer (MMA), 2-ethylhexyl acrylate monomer (2-EHAM), and methacrylic acid (MAAC); No. 7 silica sand 90-110 parts by weight; 10 to 20 parts by weight of ordinary cement; 10 to 20 parts by weight of the organic-inorganic hybrid hollow nanoparticles; It is characterized in the technical configuration that the waterproofing material composition comprising an appropriate amount of water is applied and formed by thermocompression curing.

The hydration adhesive binder is 860 parts by weight of water, 388 parts by weight of methyl methacrylate monomer (MMA), 526 parts by weight of 2-ethylhexyl acrylate monomer (2-EHAM), and 36 parts by weight of methacrylic acid (MAAC) and 17.4 parts by weight of a 30% aqueous hydrochloric acid solution, 10 parts by weight of a reactive emulsifier represented by the following [Formula 1], and 2.6 parts by weight of ammonium persulfate (APS) as a radical polymerization initiator and sodium metabisulfite (Sodium metabisulfite; A composition comprising 2.5 parts by weight of SMBS, 0.6 parts by weight of sodium bicarbonate as an alkalizing agent and 0.4 parts by weight of tert-butyl hydroperoxide (t-BHP) as a polymerization accelerator is radically polymerized. It is characterized by the technical structure that it is a polymerization composition.

[Formula 1]

(Wherein, R is an alkyl group, and X is -SO ₃ NH ₄ or -SO ₃ Na)

A mortar layer or a ready-mixed concrete layer is poured on the organic-inorganic hybrid waterproofing layer, so that the organic-inorganic hybrid waterproofing layer is integrally combined with the mortar or ready-mixed concrete layer, and the lower part of the moisture-blocking cut-off film is in contact with the concrete substrate to form a waterproof structure. It is characterized by the technical composition.

After the hydration adhesive binder is cured by coating the No. 7 silica sand and ordinary cement particles, the No. 7 silica sand is hydrated by alkali and water of the mortar layer or the ready-mixed concrete layer poured on the organic-inorganic hybrid waterproofing material layer, and the coating is peeled off. And by exposing the ordinary cement particles to be integrally combined with the mortar layer or the ready-mixed concrete layer, the organic-inorganic hybrid waterproofing material layer and the mortar layer or the ready-mixed concrete layer are not separated from each other.

The organic-inorganic hybrid waterproofing material layer blocks heat by heat shielding and thermal insulation by the hollow core part of the organic-inorganic hybrid hollow nanoparticles and kinetic energy conversion of the heat absorbed by the first coating layer, resulting from thermal aging It is characterized in the technical configuration to prevent the separation of the organic-inorganic hybrid waterproofing layer and the mortar layer or the ready-mixed concrete layer or the separation of the moisture barrier cut-off film from the concrete substrate.

It is characterized in the technical configuration that the nonwoven fabric is further laminated on the lower surface of the moisture barrier cut-off film layer.

It is characterized in the technical configuration that a polyurethane layer is further formed on the lower surface of the moisture barrier cut-off film layer.

The moisture barrier cut-off film layer is selected from a hot melt polyester film, a hot melt polyethylene film, a hot melt polypropylene film, or a hot melt polyurethane film and is thermally deposited on the nonwoven fabric.

In addition, the present invention comprises the steps of pre-treating the concrete substrate to be waterproofed; attaching a composite waterproofing sheet in which an organic-inorganic hybrid waterproofing material layer containing the organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated to the pretreated concrete substrate; A waterproof construction method using a composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated, including the step of pouring mortar or ready-mixed concrete on the composite waterproof sheet characterized by

After the step of pre-treating the concrete substrate, in order to reinforce the adhesion of the bottom surface of the composite waterproof sheet in which the concrete substrate and the organic-inorganic hybrid waterproofing layer containing the organic-inorganic hybrid hollow nanoparticles and the cut-off film deposition nonwoven fabric are laminated, the pre-treated It is characterized in that it includes the step of applying a self-leveling agent, an adhesive primer or a polyurethane paint to the concrete substrate.

Hereinafter, embodiments and/or drawings of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms, and is not limited to the embodiments and/or drawings described herein.

First, the composite waterproof sheet in which the organic-inorganic hybrid waterproofing material layer and the cut-off film deposition nonwoven fabric are laminated with the organic-inorganic hybrid hollow nanoparticles of the present invention, as shown in [Fig. a moisture barrier cut-off film layer 103; The organic-inorganic hybrid waterproofing material layer 101 containing organic-inorganic hybrid hollow nanoparticles on the upper surface of the nonwoven fabric 102; is formed to include, and is formed to block and insulate heat by the organic-inorganic hybrid hollow nanoparticles, and to convert kinetic energy of absorbed heat It is configured to block heat by

More specifically, the organic-inorganic hybrid hollow nanoparticles function to block heat by heat shielding, thermal insulation, and kinetic energy conversion of absorbed heat. Here, the organic-inorganic hybrid hollow nanoparticles are the same as those mentioned in Patent Application No. 10-2020-0024161, filed on February 27, 2020 by the present applicant.

That is, the organic-inorganic hybrid hollow nanoparticles include a hollow core portion; and a shell part surrounding the core part and formed of a plurality of coating layers, wherein the shell part is provided adjacent to the core part and is formed on the first coating layer and a first coating layer for converting thermal energy absorbed from the outside into kinetic energy. However, it is configured to include a second coating layer located at the outermost part to block heat by heat shielding and thermal insulation by the hollow core part and kinetic energy conversion of heat absorbed by the first coating layer, and the particle size is 200 It is spherical with a diameter of ~300 nm.

Referring to FIG. 2 , the core part 10 of the organic-inorganic hybrid hollow nanoparticles is located in the center of the hollow nanoparticles 100 and is formed in a hollow hollow shape. The shell part 20 includes a first coating layer 21 formed to surround the entire surface of the core part 10 and a second coating layer 22 formed on the first coating layer 21 .

The first coating layer 21 is a layer that serves as a heat exchange layer that converts heat energy absorbed from the outside into kinetic energy by contracting and relaxing, and is a thermoplastic polymer, specifically polystyrene, polyethylene, polypropylene ( polypropylene), polyvinyl chloride (Polyvinylchlorid), polyester, may be one or more selected from the group consisting of polyacrylate and polyamide, preferably polystyrene (polystyrene) may be .

At this time, it is preferable that the thickness of the first coating layer 21 is 1 nm to 50 nm, and if the thickness of the first coating layer 21 is less than 1 nm, the heat exchange efficiency is low, and when it exceeds 50 nm, the overall size of the nanoparticles becomes large, It is not preferable because durability may be reduced.

The second coating layer 22 is a layer formed on the outermost layer of the hollow nanoparticles 100 for excellent durability such as stability, heat resistance, and water resistance of the hollow nanoparticles 100 or the first coating layer 21, silicon composite oxide or silicon oxide. Specifically, the second coating layer 22 is silica (Silica), quartz (SiO ₂ ), silicon (Si), gold (Ag), platinum (Pt), silver (Ag), copper (Cu), cobalt (Co), at least one selected from the group consisting of iron (Fe), nickel (Ni), manganese (Mn), zinc (Zn), molybdenum (Mo), chromium (Cr), and oxides thereof, preferably silica (Silica ), quartz (SiO ₂ ), and silicon (Si) is at least one selected from the group consisting of.

The second coating layer 22 may include a plurality of pores, and thus, material movement is easy and molecular behavior is smooth, so that applications and applications in more diverse fields may be possible.

On the other hand, the second coating layer 22 is gold (Ag), platinum (Pt), silver (Ag), copper (Cu), cobalt (Co), iron (Fe), nickel (Ni), It may have a structure doped with one or more metals selected from the group consisting of manganese (Mn), zinc (Zn), molybdenum (Mo) and chromium (Cr), wherein the silicon oxide is silica (Silica), quartz (SiO ₂ ), and may be at least one selected from the group consisting of silicon (Si).

The organic-inorganic hybrid hollow nanoparticles 100 are prepared by manufacturing a silica core (S10), forming a first coating layer by coating a thermoplastic polymer on the silica core (S20), etching the silica core ( S30) and coating an inorganic oxide on the first coating layer to form a second coating layer (S40).

[Figure 3] is a process diagram for explaining the method of manufacturing the organic-inorganic hybrid hollow nanoparticles.

Referring to [Fig. 3], first, it is a step (S10) of preparing a silica core. In the silica core preparation, the silica precursor is dispersed in a solvent for 10 to 30 minutes, preferably for 20 minutes, and a base catalyst is added so that the pH is 9 or less, preferably the pH is 11 for 30 to 90 minutes, preferably is stirred for 1 hour, then mixed and stirred for 10 to 60 minutes, preferably 30 minutes by adding an acid catalyst, washed with purified water and dried at 100 to 140 ° C., preferably 120 ° C. for 1 hour A silica core is prepared.

At this time, when the pH is lower than 9, crystallization occurs quickly as the amount of cations increases, which may act as an impurity of the sample, and it is not preferable because it may decrease the solubility of the silica precursor and cause non-uniformity.

By controlling the pH as well as the above-mentioned pH as well as the stirring time and the addition amount of the acid catalyst, the rate of growth into the silica core can be varied by controlling the collision frequency of silicon ions differently, thereby preparing silica cores having various particle sizes. can

As the silica precursor, tetraethylorthosilicate (TEOS), glycidyloxypropyl trimethoxysilane (3-glycidyloxylpropyl trimethoxysilane, GPTMS), methyl-triethoxysilane (MTEOS), tetraproxysilane (tetraproxysilane), tetrabutoxysilane (tetrabutoxysilane) and at least one selected from the group consisting of sodium silicate, preferably tetraethylorthosilicate (TEOS) can be used, but is not limited thereto .

The solvent may be at least one selected from the group consisting of purified water, ethanol, methanol, propanol and butanol, preferably ethanol, and most preferably 50 to 100% ethanol.

The acid catalyst is hydrochloric acid (HCl), sulfuric acid (H ₂ SO ₄ ), fluorosulfuric acid (CF ₃ SO ₃ H), nitric acid (HNO ₃ ), phosphoric acid (H ₃ PO ₄ ), acetic acid (C ₂ H ₄ O ₂ ) , as hexafluorophosphoric acid (H ₃ OPF ₆ ), p-Toluene Sulfonic Acid (C ₇ H ₈ O ₃ SH ₂ O) and trifluoromethanesulphonic acid (CF ₃ SO ₃ H) At least one selected from the group consisting of, preferably hydrochloric acid, the basic catalyst is ammonium hydroxide (NH ₄ OH), lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide ( RbOH), and at least one selected from the group consisting of cesium hydroxide (CsOH), preferably ammonium hydroxide (NH ₄ OH).

Then, a first coating layer is formed by coating a thermoplastic polymer on the silica core (S20). After adding an initiator and purified water to the silica core prepared in step S10 and mixing for 5 to 10 minutes, a thermoplastic polymer is added to 500 to 1000 rpm, preferably at a temperature of 50 to 200 ° C, preferably 80 to 100 ° C. Preferably, it is reacted at a speed of 600 to 800 rpm for 8 to 20 hours, preferably for 10 to 14 hours to prepare particles having a core-shell structure in which the silica core has a first coating layer.

At this time, if the reaction temperature is less than 50 ℃, polymerization reaction is difficult to occur, and if it exceeds 200 ℃, it may cause a change in physical properties. In addition, if the stirring rate is less than 500 rpm, the reaction rate may occur slowly, and if it exceeds 1000 rpm, the efficiency due to unnecessary increase in the stirring rate may not be very high.

If the reaction time is less than 8 hours, the time is insufficient for the polymerization reaction to be completed.

As the initiator, azobis dihydrochloride (2,2'-azobis dihydrochloride) may be used.

The thermoplastic polymer is selected from the group consisting of polystyrene, polyethylene, polypropylene, polyvinylchlorid, polyester, polyacrylate and polyamide. It may be one or more, preferably polystyrene.

Next, the silica core is etched and removed from the particles having a core-shell structure in which the first coating layer is provided on the silica core prepared in step S20. That is, a weak base solution can be applied so that only the silica core can be selectively removed from the core-shell particles of step S20, and specifically, selected from the group consisting of sodium hydroxide (NaOH) and potassium hydroxide (KOH). At least one, preferably sodium hydroxide (NaOH), most preferably 20 to 70% sodium hydroxide (NaOH) may be added and stirred for 20 to 30 hours, preferably 22 to 26 hours. If a basic solution with too high a concentration is used, it is not preferable because safety problems may occur in the process.

For example, by mixing and stirring the core-shell particles with a weak base solution, the silica core can be selectively removed by forming a soluble silicate by alkali melting.

As the first coating layer from which the silica core is removed is formed in this way, solar thermal energy absorbed from the outside, such as ultraviolet rays, is converted into kinetic energy of contraction and expansion of the first coating layer, thereby consuming heat, thereby exhibiting a heat shielding effect. The swelling of the material can be suppressed, and the material is not damaged, so it can be used continuously for a long time.

Finally, an inorganic oxide is coated on the first coating layer to form a second coating layer (S40). In the step S30, the silica core is removed and the particles remaining only the first coating layer are dispersed in a solvent, an inorganic oxide is added and stirred for 40 to 100 minutes, preferably 50 to 70 minutes, and then a basic catalyst is added to 8 to 20 A second coating layer may be formed on the first coating layer by reacting for a period of time, preferably 10 to 14 hours.

The inorganic oxide and the basic catalyst may be mixed in a weight ratio of 1:1 to 20, preferably 1:5 to 15 by weight, and the particle porosity and specific surface area of the second coating layer according to the mixing weight ratio of the inorganic oxide and the basic catalyst can be adjusted.

The solvent may be at least one selected from the group consisting of purified water, ethanol, methanol, propanol and butanol, preferably ethanol, and most preferably 10-80% ethanol.

The inorganic oxide is silica (Silica), quartz (SiO ₂₎ , silicon (Si), gold (Ag), platinum (Pt), silver (Ag), copper (Cu), cobalt (Co), iron (Fe), Nickel (Ni), manganese (Mn), zinc (Zn), molybdenum (Mo), chromium (Cr), tetraethylorthosilicate (TEOS), 3-glycidyloxylpropyl trimethoxysilane, GPTMS), methyl-triethoxysilane (MTEOS), tetraproxysilane, tetrabutoxysilane, sodium silicate, and one selected from the group consisting of oxides thereof can be more than

The basic catalyst is one selected from the group consisting of ammonium hydroxide (NH ₄ OH), lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), and cesium hydroxide (CsOH) Above, preferably ammonium hydroxide (NH ₄ OH) may be.

As described above, since the second coating layer is formed on the first coating layer, not only surface adhesion but also surface hardness and durability may be further improved, and deterioration may be prevented by assisting the heat exchange movement of the first coating layer.

On the other hand, the organic-inorganic hybrid waterproofing material layer is ethylene vinyl acetate (EVA) 60 to 80 parts by weight; 5 to 15 parts by weight of a hydration adhesive binder comprising methyl methacrylate monomer (MMA), 2-ethylhexyl acrylate monomer (2-EHAM), and methacrylic acid (MAAC); No. 7 silica sand 90-110 parts by weight; 10 to 20 parts by weight of ordinary cement; 10 to 20 parts by weight of the organic-inorganic hybrid hollow nanoparticles; An appropriate amount of water; is formed by applying a waterproofing composition comprising a composition, thermocompression bonding and curing.

At this time, the hydration adhesive binder contains 860 parts by weight of water, 388 parts by weight of methyl methacrylate monomer (MMA), 526 parts by weight of 2-ethylhexyl acrylate monomer (2-EHAM), and 36 parts by weight of methacrylic acid (MAAC). 17.4 parts by weight of a 30% aqueous hydrochloric acid solution, 10 parts by weight of a reactive emulsifier represented by the following [Formula 1], and 2.6 parts by weight of ammonium persulfate (APS) as a radical polymerization initiator and sodium metabisulfite (Sodium) A composition comprising 2.5 parts by weight of metabisulfite (SMBS), 0.6 parts by weight of sodium bicarbonate as an alkalizing agent, and 0.4 parts by weight of tert-butyl hydroperoxide (t-BHP) as a polymerization accelerator, radically It is a polymerized composition.

[Formula 1]

(Wherein, R is an alkyl group, and X is -SO ₃ NH ₄ or -SO ₃ Na)

The methyl methacrylate monomer (MMA) used in the hydration adhesive binder of the organic-inorganic hybrid waterproofing material layer is a colorless and transparent liquid that is prepared by using C4 oil as a raw material and tert-butyl alcohol (TBA) in a gaseous state. It is a reactive resin prepared by oxidizing methacrylic acid to produce methacrylic acid and then esterifying with methanol, that is, a reaction-type resin made to have double carbon bonds through a polymerization reaction process of acrylic acid and mithaacrylic acid ester, CH2=C(CH3)CO2CH3 has a chemical formula

The methyl methacrylate monomer (MMA) is of a hard type and flexible, and when radical polymerization at a low temperature, the ratio of the syndiotactic structure showing continuous regularity of the polymer chain structure is increased. , heat resistance, chemical resistance, abrasion resistance, UV safety, etc., and excellent weather resistance, which is a property to withstand weather and climate such as sunlight, inhibits corrosion caused by external environmental changes (weather and climate change) and penetrates into the package It is integrated to improve adhesion strength and toughness, has good colorability by pigments, etc., has a high coefficient of thermal expansion, but is a highly stable resin, so it is used in many fields because of its excellent transparency, weather resistance, and colorability.

However, MMA starts curing when a small amount of curing agent is added about 2 to 5% of the resin amount. This is excellent, so it can be installed and finished over a large area. When such MMA is used as a waterproofing composition, the strength after curing is very excellent, but it lacks crack resistance and bending followability, and the thermal expansion characteristics with the substrate are different. Due to this, there was a problem that cracks are easy to occur when used outdoors instead of indoors.

In the present invention, a polymerization composition obtained by radical polymerization by mixing methyl methacrylate monomer (MMA) with 2-ethylhexyl acrylate monomer (2-EHAM) and methacrylic acid (MAAC) to compensate for the disadvantages of MMA is used.

The 2-ethylhexyl acrylate monomer (2-EHAM) and methacrylic acid (MAAC) are mixed and used to complement the crack resistance of methyl methacrylate monomer (MMA) with ductile properties after curing.

At this time, in the radical polymerization of methyl methacrylate monomer (MMA), 2-ethylhexyl acrylate monomer (2-EHAM) and methacrylic acid (MAAC) of the hydration adhesive binder, the reactive emulsifier represented by [Formula 1] It is characterized by use.

That is, the reactive emulsifier represented by [Formula 1] is a reactive surfactant having a radical group in the molecule, and the methyl methacrylate monomer (MMA), 2-ethylhexyl acrylate monomer (2-EHAM) and Polymerization composition by stably emulsifying methacrylic acid (MAAC) as well as direct radical polymerization with the methyl methacrylate monomer (MMA), 2-ethylhexyl acrylate monomer (2-EHAM) and methacrylic acid (MAAC) It improves water resistance and physical properties, and has an excellent effect in improving waterproofness.

In addition, ethylene vinyl acetate (EVA) used in the organic-inorganic hybrid waterproofing layer is to improve the strength, adhesion, and waterproofing properties of the waterproofing layer. Performance, elasticity and waterproof performance can be improved.

In another aspect of the present invention, a mortar layer or a ready-mixed concrete layer is poured on the organic-inorganic hybrid waterproofing layer, so that the organic-inorganic hybrid waterproofing layer is integrally combined with the mortar or ready-mixed concrete layer, and the moisture blocking cut-off film lower part is concrete It is characterized by forming a waterproof structure in contact with the substrate.

Here, as another feature of the present invention, the hydration adhesive binder is coated with the No. 7 silica sand and ordinary cement particles and cured, and then the organic-inorganic hybrid waterproofing material layer is poured over the alkali and ready-mixed concrete layers. The organic/inorganic hybrid waterproofing material layer and the mortar layer or the ready-mixed concrete layer are not separated by being hydrated by water and the coating is peeled off to expose the No. 7 silica sand and ordinary cement particles to be combined with the mortar layer or the ready-mixed concrete layer. .

That is, the radical polymer of methyl methacrylate monomer (MMA), 2-ethylhexyl acrylate monomer (2-EHAM) and methacrylic acid (MAAC) of the hydration adhesive binder is coated with the No. 7 silica sand and ordinary cement particles. After curing, the acrylic polymer coating is broken by hydrating by alkali and water of the mortar layer or the ready-mixed concrete layer poured on the organic-inorganic hybrid waterproofing layer, exposing the No. 7 silica sand and ordinary cement particles to the mortar layer or the ready-mixed concrete layer and The No. 7 silica sand and ordinary cement particles are cement-bonded so that they are integrally bonded and the layers are not separated.

In addition, in another aspect of the present invention, the organic-inorganic hybrid waterproofing material layer is heat shielding and thermal insulation by the hollow core part of the organic-inorganic hybrid hollow nanoparticles and kinetic energy conversion of heat absorbed by the first coating layer. It is characterized by preventing the separation of the organic-inorganic hybrid waterproofing layer and the mortar layer or the ready-mixed concrete layer or the separation of the moisture blocking cut-off film from the concrete substrate, which occurs due to thermal aging by blocking heat.

In addition, the moisture barrier cut-off film layer 103 is selected from a hot melt polyester film, a hot melt polyethylene film, a hot melt polypropylene film or a hot melt polyurethane film to be thermally deposited on the nonwoven fabric 102 .

In this case, a nonwoven fabric may be further laminated or a polyurethane layer may be further formed on the lower surface of the moisture barrier cut-off film layer.

The moisture barrier cut-off film layer may be selected from a hot melt polyester film, a hot melt polyethylene film, a hot melt polypropylene film or a hot melt polyurethane film and thermally deposited on the nonwoven fabric.

On the other hand, the waterproof construction method using a composite waterproofing sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles of the present invention and a cut-off film deposition nonwoven fabric are laminated includes the steps of pre-treating a concrete substrate to be waterproofed; attaching a composite waterproofing sheet in which an organic-inorganic hybrid waterproofing material layer containing the organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated to the pretreated concrete substrate; It can be constructed by a construction method comprising; pouring mortar or ready-mixed concrete on the composite waterproof sheet.

At this time, after the step of pre-treating the concrete substrate, the organic-inorganic hybrid waterproofing layer containing the concrete substrate and the organic-inorganic hybrid hollow nanoparticles and the cut-off film deposition nonwoven fabric are laminated to reinforce the adhesion of the bottom surface of the composite waterproof sheet. It may include applying a self-leveling agent, an adhesive primer, or a polyurethane paint to the pretreated concrete substrate.

In addition, the composite waterproof sheet in which the organic-inorganic hybrid waterproofing material layer containing the organic-inorganic hybrid hollow nanoparticles of the present invention and the cut-off film deposition nonwoven fabric are laminated is, as shown in [Fig. A nonwoven fabric drawn in from a nonwoven fabric roll is laminated on the blocking cut-off film, and an organic-inorganic hybrid waterproofing material containing organic-inorganic hybrid hollow nanoparticles is put on the upper surface of the nonwoven fabric and applied to a certain thickness and width by an application knife, and then continuously It can be manufactured by a Concurrent Multi-layer Process process and device that is dried by thermocompression bonding while passing through a thermal dryer and rolling rolls.

[Production of organic-inorganic hybrid hollow nanoparticles of the present invention]

After adding 10 g of TEOS to 95% ethanol and stirring for 2 minutes, 15 mL of aqueous ammonia solution was added so that the pH became 11, followed by stirring for 1 hour. Then, 1 mL of hydrochloric acid was added, stirred for 30 minutes, washed with purified water, and dried at 120° C. for 1 hour to obtain a silica core. A transmission electron microscope image of the obtained silica core is shown in FIG. 5 .

7.0 g of silica core was placed in a mixture of 17 mL of purified water and 0.5 g of AIBA (2,2'-azobis dihydrochloride), stirred for 10 minutes, and then 0.5 mL of styrene was added dropwise. Then, the mixture was reacted at 90° C. at 700 rpm for 12 hours to obtain 6 g of polystyrene-coated core-shell particles on a silica core. A transmission electron microscope image of the obtained core-shell particles is shown in [FIG. 5].

The polystyrene-coated silica core was placed in 150 mL of 25% sodium hydroxide, stirred for 24 hours, and washed with purified water to obtain 3 g of hollow polystyrene particles in which only the polystyrene coating layer remained. A transmission electron microscope image of the obtained hollow polystyrene particles is shown in FIG. 7 .

After mixing the hollow polystyrene particles in 500 mL of purified water and 300 mL of ethanol, 10 mL of TEOS was added dropwise and stirred for 60 minutes, then 10 mL of aqueous ammonia solution was added and stirred for 12 hours. Then, it was washed with purified water and dried at 80° C. for 12 hours to obtain hollow double-shell particles in which a silicon dioxide coating layer was formed on the polystyrene coating layer. Finally, a transmission electron microscope image of the organic-inorganic hybrid hollow nanoparticles of the present invention is shown in FIG. 8 .

[Production of organic-inorganic hybrid waterproof sheet of the present invention]

① Manufacture of hydration adhesive binder

In a detachable flask, 520 parts by weight of ion-exchanged water, 3.4 parts by weight of a 30% hydrochloric acid solution, and 0.6 parts by weight of sodium bicarbonate as an alkalinizing agent were added, the temperature was raised to 65° C., and the mixture was stirred and replaced with nitrogen.

Then, in a separate container, 340 parts by weight of ion-exchanged water, 14 parts by weight of a 30% hydrochloric acid solution, 10 parts by weight of a reactive emulsifier (trade name SR10), 388 parts by weight of methyl methacrylate monomer (MMA), 2-ethylhexyl acrylate monomer (2-EHAM) 526 parts by weight and methacrylic acid (MAAC) 36 parts by weight were added, the temperature was raised to 75° C. and emulsified while stirring, and the emulsion was continuously dripped into the above-described separable flask. Moreover, while nitrogen gas was introduce|transduced into a separable flask during dripping, the internal temperature was maintained at 75 degreeC. After the continuous dripping was completed, it was aged for 1 hour.

Then, 2.6 parts by weight of ammonium persulfate (APS) and 2.5 parts by weight of sodium metabisulfite (SMBS) as a radical polymerization initiator, tert-butyl hydroperoxide (T-BHP) as a polymerization accelerator ) 0.4 parts by weight, 0.002 parts by weight of an aqueous solution of ferrous sulfate (FeSO4) as a pH adjuster, and 16 parts by weight of 25%-NH4OH as a neutralizing agent were added for radical polymerization to obtain a hydroadhesive binder polymer solution of the present invention.

② Preparation of organic-inorganic hybrid waterproofing material composition

5 parts by weight of water; 70 parts by weight of ethylene vinyl acetate (EVA), 10 parts by weight of the hydroadhesive binder polymer solution prepared above, 100 parts by weight of silica sand No. 7, 10 parts by weight of ordinary cement, and 20 parts by weight of organic-inorganic hybrid hollow nanoparticles prepared in [Example 1] The waterproofing material composition of the present invention was prepared by homogeneously mixing parts by weight.

③ Manufacturing of organic-inorganic hybrid waterproof sheet

The nonwoven fabric drawn in from the nonwoven fabric roll is laminated on top of the moisture barrier cutoff film introduced from the moisture barrier cutoff film roll, and the organic-inorganic hybrid waterproofing composition comprising the organic-inorganic hybrid hollow nanoparticles of the present invention prepared above on the upper surface of the nonwoven fabric is added The organic-inorganic hybrid hollow of the present invention by the Concurrent Multi-layer Process and device, which is applied to a certain thickness and width with an application knife and then dried by thermal compression while continuously passing through a thermal dryer and rolling roll. An organic-inorganic hybrid waterproof sheet containing nanoparticles was prepared.

④ Preparation of Comparative Example 1

[Comparative Example 1] was prepared in the same manner as [Example 1] except for the organic-inorganic hybrid hollow nanoparticles in the organic-inorganic hybrid waterproof sheet of the present invention prepared in [Example 1].

[The thermal barrier performance test of the organic-inorganic hybrid waterproof sheet of the present invention]

The organic-inorganic hybrid waterproof sheet prepared in [Example 1] and [Comparative Example 1] was attached to the surface of the rooftop concrete, and the surface temperature was measured every hour, and the results are shown in [Table 1].

thermal condition Temperature (℃) time Temperature (℃) Example 1 Comparative Example 1 9 o'clock 21 2 5 10 o'clock 23 8 10 11 o'clock 26 16 25 12 o'clock 26 20 32 13:00 27 24 33 14 o'clock 28 28 35 15:00 28 30 35 16:00 28 30 33 17:00 26 28 30 18:00 25 26 30

As shown in [Table 1], the organic-inorganic hybrid waterproof sheet containing the organic-inorganic hybrid hollow nanoparticles of the present invention has a much lower surface temperature than the organic-inorganic hybrid waterproof sheet that does not contain the hollow nanoparticles, so that the heat blocking It can be seen that the effect is excellent.

The above description is merely illustrative of the technical idea of the present invention, and various modifications and variations will be possible without departing from the essential characteristics of the present invention by those skilled in the art to which the present invention pertains. Accordingly, the embodiments and/or drawings disclosed in the present invention are not intended to limit the technical spirit of the present invention but to explain, and the scope of the technical spirit of the present invention is not limited by these embodiments and/or drawings. . The protection scope of the present invention should be construed by the following claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

10: core part 20: shell part
21: first coating layer 22: second coating layer
100: nanoparticles 101: organic-inorganic hybrid waterproofing material layer
102: nonwoven fabric 103: moisture barrier cut-off film layer

Claims (15)

A moisture barrier cut-off film is deposited on the bottom surface of the nonwoven fabric, and an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles is formed on the upper surface of the nonwoven fabric, so that heat shielding and insulation by the organic-inorganic hybrid hollow nanoparticles and kinetic energy of absorbed heat Block heat by transformation,
The organic-inorganic hybrid hollow nanoparticles include a hollow core portion; and a shell part surrounding the core part and formed of a plurality of coating layers, wherein the shell part is provided adjacent to the core part and is formed on the first coating layer and a first coating layer for converting thermal energy absorbed from the outside into kinetic energy. However, it is configured to include a second coating layer located at the outermost part to block heat by heat shielding and thermal insulation by the hollow core part and kinetic energy conversion of heat absorbed by the first coating layer,
The organic-inorganic hybrid waterproofing material layer includes 60 to 80 parts by weight of ethylene vinyl acetate (EVA); 5 to 15 parts by weight of a hydration adhesive binder comprising methyl methacrylate monomer (MMA), 2-ethylhexyl acrylate monomer (2-EHAM), and methacrylic acid (MAAC); No. 7 silica sand 90-110 parts by weight; 10 to 20 parts by weight of ordinary cement; 10 to 20 parts by weight of the organic-inorganic hybrid hollow nanoparticles; It is formed by coating, thermocompression bonding, and curing a waterproofing material composition comprising water;
The hydration adhesive binder is 860 parts by weight of water, 388 parts by weight of methyl methacrylate monomer (MMA), 526 parts by weight of 2-ethylhexyl acrylate monomer (2-EHAM), and 36 parts by weight of methacrylic acid (MAAC) and 17.4 parts by weight of a 30% aqueous hydrochloric acid solution, 10 parts by weight of a reactive emulsifier represented by the following [Formula 1], and 2.6 parts by weight of ammonium persulfate (APS) as a radical polymerization initiator and sodium metabisulfite (Sodium metabisulfite; A composition comprising 2.5 parts by weight of SMBS, 0.6 parts by weight of sodium bicarbonate as an alkalizing agent and 0.4 parts by weight of tert-butyl hydroperoxide (t-BHP) as a polymerization accelerator is radically polymerized. Composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles, characterized in that it is a polymer composition, and a cut-off film deposition nonwoven fabric are laminated
[Formula 1]

(Wherein, R is an alkyl group, and X is -SO ₃ NH ₄ or -SO ₃ Na)
delete According to claim 1,
The first coating layer of the organic-inorganic hybrid hollow nanoparticles is an organic-inorganic hybrid hollow, characterized in that at least one selected from the group consisting of polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyester, polyacrylate and polyamide A composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing nanoparticles and a cut-off film deposition nonwoven fabric are laminated
According to claim 1,
The second coating layer is characterized in that at least one selected from the group consisting of silica, quartz, silicon, gold, platinum, silver, copper, cobalt, iron, nickel, manganese, zinc, molybdenum, chromium and oxides thereof A composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing organic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated
According to claim 1,
The organic-inorganic hybrid hollow nanoparticles are spherical having a diameter of 200 to 300 nm, and the organic-inorganic hybrid waterproofing layer comprising organic-inorganic hybrid hollow nanoparticles, characterized in that the first coating layer has a thickness of 1 to 50 nm; Composite waterproof sheet laminated with cut-off film deposition non-woven fabric
delete delete According to claim 1,
A mortar layer or a ready-mixed concrete layer is poured on the organic-inorganic hybrid waterproofing material layer, the organic-inorganic hybrid waterproofing material layer is integrally combined with the mortar layer or the ready-mixed concrete layer, and the lower part of the moisture-blocking cut-off film is in contact with the concrete substrate to form a waterproof structure. A composite waterproofing sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated
According to claim 1,
After the hydration adhesive binder is cured by coating the No. 7 silica sand and ordinary cement particles, the No. 7 silica sand is hydrated by alkali and water of the mortar layer or the ready-mixed concrete layer poured on the organic-inorganic hybrid waterproofing material layer. and organic-inorganic hybrid hollow nanoparticles, characterized in that the organic-inorganic hybrid waterproofing material layer and the mortar layer or the ready-mixed concrete layer are not separated by exposing the ordinary cement particles to be integrally combined with the mortar layer or the ready-mixed concrete layer Composite waterproof sheet laminated with organic-inorganic hybrid waterproofing material layer and cut-off film deposition nonwoven fabric
9. The method of claim 8,
The organic-inorganic hybrid waterproofing material layer is generated by thermal aging by blocking heat by heat shielding and thermal insulation by the hollow core part of the organic-inorganic hybrid hollow nanoparticles and kinetic energy conversion of heat absorbed by the first coating layer Organic-inorganic hybrid waterproofing material comprising organic-inorganic hybrid hollow nanoparticles, characterized in that it prevents the separation of the organic-inorganic hybrid waterproofing layer and the mortar layer or the ready-mixed concrete layer or the separation of the moisture blocking cut-off film from the concrete substrate Composite waterproof sheet laminated with a layer and a cut-off film deposition nonwoven fabric
According to claim 1,
A composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated, characterized in that a nonwoven fabric is further laminated on the lower surface of the moisture barrier cut-off film layer
According to claim 1,
A composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated, characterized in that a polyurethane layer is further formed on the lower surface of the moisture barrier cut-off film layer
According to claim 1,
The moisture barrier cut-off film layer is selected from a hot melt polyester film, a hot melt polyethylene film, a hot melt polypropylene film, or a hot melt polyurethane film organic-inorganic hybrid organic-inorganic hybrid comprising hollow nanoparticles, characterized in that it is thermally deposited on the nonwoven fabric Composite waterproof sheet laminated with waterproof material layer and cut-off film deposition non-woven fabric
pre-treating the concrete substrate to be waterproofed; An organic-inorganic hybrid waterproofing material layer and a cut-off film deposition nonwoven fabric comprising organic-inorganic hybrid hollow nanoparticles according to any one of claims 1, 3 to 5, and 8 to 13 on the pretreated concrete substrate attaching the laminated composite waterproof sheet; Pouring mortar or ready-mixed concrete on top of the composite waterproof sheet; waterproof construction using a composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated, comprising: Method
15. The method of claim 14,
After the step of pre-treating the concrete substrate, to reinforce the adhesion of the bottom surface of the composite waterproof sheet on which the concrete substrate and the organic-inorganic hybrid waterproofing layer containing the organic-inorganic hybrid hollow nanoparticles and the cut-off film deposition non-woven fabric are laminated, the pre-treated A composite waterproof sheet in which an organic-inorganic hybrid waterproofing material layer containing organic-inorganic hybrid hollow nanoparticles and a cut-off film deposition nonwoven fabric are laminated, comprising the step of applying a self-leveling agent, an adhesive primer, or a polyurethane paint to a concrete substrate Waterproof construction method using

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