WO2021215645A1 - Fire extinguishing film comprising fire extinguishing microcapsule, and manufacturing method therefor - Google Patents

Abstract

The present invention relates to a fire extinguishing film including a fire extinguishing microcapsule, and a manufacturing method therefor. The fire extinguishing film comprises a core-shell structure capsule and a photocurable resin. The core contains a fire extinguishing agent. Accordingly, the fire extinguishing film provides an effect capable of preventing or extinguishing a fire in various extremely small spaces.

Description

Digestive film containing microcapsules for fire extinguishing and method for manufacturing the same

The present invention relates to a fire extinguishing film comprising microcapsules for fire extinguishing and a method for manufacturing the same, wherein the fire extinguishing film comprises a capsule having a core-shell structure and a photocurable resin, and wherein the core comprises a fire extinguishing agent do it with Accordingly, the fire extinguishing film provides the effect of preventing or suppressing a fire in a variety of very small spaces.

Encapsulation is a physico-chemical process in which a liquid, solid or gas as a core and a shell surrounding the outside of the core are formed. prevent interaction. The main purpose of such encapsulation is the controlled external release of the encapsulated core, in which case the encapsulated core generally requires complete isolation from the outside during storage and processing steps.

In addition, the external release of the core according to the encapsulation may vary depending on the intended use. For example, to take advantage of the controlled external release of the core that is released from the shell, the core can be encapsulated and used in drugs, pesticides, fragrances and mineral fertilizers. Among the various uses of such encapsulation, in particular, the technology of extinguishing a fire by releasing the fire extinguishing agent to the outside as the shell is destroyed in case of a fire by including the core as a fire extinguishing agent is desperately needed in the modern society where a lot of electronic and electrical appliances are used. Various technologies are being developed according to the demand.

For example, fire extinguishing microcapsules have a fire extinguishing agent as the core and are encapsulated inside the shell. When a fire occurs, the extinguishing agent leaves the shell within a short time in a narrow temperature range. It can speed up fire suppression and improve the efficiency of fire suppression. However, these microcapsules for fire extinguishing are greatly affected by the external environment, and when the shell is destroyed by external force or environment and the fire extinguishing agent, which is the core, is released to the outside, the amount of extinguishing agent required for fire extinguishing is small at the moment when fire is needed. The problem of not meeting the concentration of the extinguishing agent may arise. Therefore, while providing an excellent extinguishing effect by securing a sufficient amount of extinguishing agent, research on a method for quickly suppressing a fire by applying various microcapsules for digestion is being actively conducted.

[Prior art literature]

[Patent Literature]

(Patent Document 1) Korean Patent Publication No. 10-1994813 (June 25, 2019)

An object of the present invention is to solve all of the above problems.

An object of the present invention is to prevent or suppress a fire by applying it to various spaces such as a very small space as well as a place where there is always a fire risk.

An object of the present invention is to effectively extinguish a fire in a short time when a fire occurs.

An object of the present invention is to provide excellent ductility and heat dissipation effect, thereby helping to prevent fire.

In order to achieve the object of the present invention as described above and to realize the characteristic effects of the present invention to be described later, the characteristic configuration of the present invention is as follows.

According to an embodiment of the present invention, it comprises a microcapsule for fire extinguishing and a photocurable resin, wherein the microcapsule for fire extinguishing has a core-shell structure, and the core contains 80 to 97% by weight of a fire extinguishing agent, and the shell A film comprising microcapsules for digestion that surrounds the silver core and contains a precipitant or coagulant with a non-porous polymer is provided.

According to an embodiment of the present invention, mixing an initiator and a monomer, preparing a photocurable resin by adding an oligomer, and an additive; preparing a photocurable resin mixture by putting microcapsules for digestion into the photocurable resin; and preparing a film by photocuring the photocurable resin mixture.

The fire extinguishing film including the fire extinguishing microcapsule according to the present invention can be applied in a place where fire risk always exists or in various spaces, thereby providing an effect of preventing or quickly suppressing a fire. In other words, when a fire occurs, the microcapsules can be ruptured simultaneously within a short time to quickly and efficiently extinguish the fire.

In particular, it can be applied to various spaces such as places where there is always a fire risk such as outlets and electric breakers, as well as very small spaces such as rechargeable batteries and electronic cigarettes.

In addition, by providing excellent ductility and heat dissipation, it can help prevent fire.

1 shows a fire extinguishing film including a fire extinguishing microcapsule according to the present invention.

2 shows a microcapsule for digestion according to the present invention.

Figure 3 shows that the adhesive layer is laminated on the fire extinguishing film including the fire extinguishing microcapsule according to the present invention.

4 shows that the release layer is laminated on the fire extinguishing film including the fire extinguishing microcapsule according to the present invention.

5 is a view showing a tape structure including a fire extinguishing film including a fire extinguishing microcapsule according to the present invention.

6 is a view showing that the heat insulating / insulating layer is laminated on the fire extinguishing film including the fire extinguishing microcapsule according to the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The detailed description of the present invention set forth below refers to, by way of illustration, specific embodiments in which the present invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the present invention. It should be understood that the various embodiments of the present invention are different but need not be mutually exclusive. For example, certain shapes, structures, and characteristics described herein with respect to one embodiment may be embodied in other embodiments without departing from the spirit and scope of the invention. In addition, it should be understood that the location or arrangement of individual components within each disclosed embodiment may be changed without departing from the spirit and scope of the present invention. Accordingly, the detailed description set forth below is not intended to be taken in a limiting sense, and the scope of the invention, if properly described, is limited only by the appended claims, along with all scope equivalents to those claimed.

According to an embodiment of the present invention, it includes a microcapsule 110 for fire extinguishing and a photocurable resin, and the microcapsule 110 for fire extinguishing has a core 111-shell 112 structure, and the core 111 contains 80 to 97% by weight of a fire extinguishing agent, the shell 112 surrounds the core 111, and a non-porous polymer film containing microcapsules 110 for fire extinguishing containing a precipitant or coagulant ( 100) is provided.

Referring to FIG. 1 , the film 100 including the fire extinguishing microcapsule 110 includes the fire extinguishing microcapsule 110 and a photocurable resin, and these are light conditions (UV, visible light, electron beam (EB)). , LED, etc.) and finally provided in the form of a film.

Referring to FIG. 2 , the fire extinguishing microcapsule 110 is formed in the form of a core 111-shell 112 in which an inner core 111 is surrounded by an outer shell 112 .

The size of the microcapsule 110 is preferably 1 to 1,000 μm, is vaporized at a specific temperature in case of fire, and may react by tearing as if the shell is ruptured by the vaporization energy of the extinguishing agent. A very small amount of extinguishing agent is ejected in one size of the microcapsule 110, but when a large number of microcapsules for extinguishing react explosively and simultaneously to eject a sufficient amount of vaporized extinguishing agent, the fire can be extinguished. can In addition, when a fire occurs, the extinguishing agent may be vaporized and expanded by heat, but does not react (rupture, leak) due to the durability and airtightness of the shell 112 formed of the non-porous polymer, and a specific temperature higher than that, In particular, in case of a fire, the extinguishing agent vaporized during the reaction acts directly on the fire ignition point and breaks the chain reaction with the four conditions of combustion: fuel (flammables), oxygen (air), heat (ignition source), and heat (ignition source) during chain reaction. can put out a fire.

In this case, the core 111 may include an extinguishing agent, and the extinguishing agent is formed to be 80 to 97% by weight of the microcapsule 110, and when included in the above range, it will provide the most excellent extinguishing effect. can

In addition, the fire extinguishing agent can be used as a material with excellent fire extinguishing performance based on a fire extinguishing agent that is not limited in production and use by the Montreal Protocol. For example, fluorine carbon, fluorine chlorine carbon, halogenated carbon from fluorine bromine carbon, halogen carbon from fluorine iodine carbon, 2-iodine-1,1,1,2,3,3,3-heptafluoropropane (HFC- 227ea) and Iodofluorocarbon (FIC-217I1 or FIC-13I1), 1,1,1,2,2-Pentafluoroethane (CF ₃ CF ₂ H, HFC-125), 1,1,1,2,3,3,3 -Heptafluoropropane (CF ₃ CHFCF ₃ ), Chlorotetrafluoroethane (CHClFCF ₃ ), fluorochemical ketone compound, dodecafluoro-2-methylpentan-3-one(FK-5-1-12, CF ₃ CF ₂ C(O)CF(CF) ₃ ) ₂ )), 1-chloro-1,2,2,2-tetrafluoroethane (C ₂ HClF ₄ ), 2-chloro-1,1,1,2-tetrafluoroethane (CHClFCF ₃ , HCFC-124), decafluoro Rocyclohexanone (perfluoro cyclohexanone), CF ₃ CF ₂ C(O)CF(CF ₃ ) ₂ (-1,1,1,2,4,4,5,5,5-nonafluoro -2-trifluoromethyl-butan- _{3one), (CF 3} ) ₂ CFC(O)CF(CF ₃ ) ₂ (-1,1,1,2,4,5,5,5,6,6 ,6,-Octafluoro-2,4,-bis(trifluoromethyl)pentan-3-one), CF ₃ CF ₂ C(O)CF ₂ CF ₂ CF ₃ , CF ₃ C(O)CF ( CF ₃ ) ₂ , 1,1,1,3,3,4,4,5,5,6,6,7,7,8,8,8,-hexadodecafluorooctan-2-one (CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ C(O)CF ₃ ), 1,1,1,3,4,4,4,-heptafluoro-3-trifluoromethylbutan-2-one ( CF ₃ C(O)CF(CF ₃ ) ₂ ), 1,1,1,2,4,4,5,5,-octafluoro-2-trifluoromethylpentan-3-one (HCF ₂ CF ₂ C(O)CF(C F ₃ ) ₂ ), 1,1,1,2,4,4,5,5,6,6,6,-undecafluoro-2-trifluoromethylhexan-3-one (CF ₃ CF ₂ CF ₂ C(O)CF(CF ₃ ) ₂ ), 1-Chloro-,1,1,3,4,4,4-hexafluoro-3-trifluoromethyl-butan-2-one ((CF ₃ ) ₂ CFC(O)CF ₂ CL), 1,1,1,2,2,4,4,5,5,6,6,6-dodecafluorohexan-3-one (CF ₃ CF ₂ C(O)CF ₂ CF ₂ CF ₃ ), 1,1,1,5,5,5,-hexafluoropentane-2-4-dione (CF ₃ C(O)CH ₂ C(O)CF ₃ ), 1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hexane-3,4-dione ((CF ₃ ) ₂ CFC(O) C(O)C(O)CF(CF ₃ ) ₂ ), 1,1,1,2,2,3,3,5,5,6,6,7,7,7,-tetradecafluoroheptane -4-one (CF ₃ CF ₂ CF ₂ C(O)CF ₂ CF ₂ CF ₃ ), 1,1,1,3,3,4,4,4-octafluorobutal-2-one (CF _{3 )} C(O)CF ₂ CF ₃ ), 1,1,2,2,4,5,5,5-octafluoro-1-trifluoromethoxy-4-trifluoromethylpentan-3-one (CF ₃ OCF ₂ CF ₂ C(O)CF(CF ₃ ) ₂ ) and 1,1,1,2,4,4,5,5,6,6,7,7,7,-tridecafluoro-2 One or more selected from -trifluoromethylheptan-3-one (CF ₃ CF ₂ CF ₂ CF ₂ C(O)CF(CF ₃ ) ₂ ) may be provided.

In addition, as a fire extinguishing agent, one of the formula C _x H _y O _z Hal _k (where x, y, z, k are natural numbers, and Hal is Br, I, F) may be used, for example, 3M's Novec 1230 (Novec 1230) may be used, but is not limited thereto.

In addition, the extinguishing agent is present in the liquid phase at room temperature, it is provided that the phase change to the gas phase at a temperature of 30 ℃ to 100 ℃. Preferably, by changing the weather at 30° C. to 60° C., when a fire occurs, the capsule ruptures to extinguish the fire.

According to an embodiment of the present invention, the shell 112 is a non-porous polymer and may include a precipitating agent or a coagulant. Based on 100 parts by weight of the non-porous polymer, 1 to 10 parts by weight of a precipitant or 1 to 10 parts by weight of a coagulant may be provided.

The shell 112 surrounds the outside of the fire extinguishing agent, which is the core 111, and serves to contain the fire extinguishing agent, and maintains weather resistance and airtightness to protect the fire extinguishing agent from leaking into the atmosphere by the external environment at normal times or up to a specific temperature. should be However, at 30° C. to 100° C., the shell may be ruptured due to the phase change from liquid to gas phase of the extinguishing agent and softening of the shell at high temperature. In this case, the shell 112 may have a thickness of 50 to 2000 nm.

In addition, in order to perform a role by a temperature reaction, the shell 112 is preferably made of a non-porous polymer. For example, polyurethane resin, polyurea resin, polyamide resin, polyester resin, polycarbonate resin, aminoaldehyde resin, melamine resin, polystyrene resin, styrene-acrylate copolymer resin, styrene-methacrylate copolymer resin , gelatin or a derivative thereof, polyvinyl alcohol, phenol formaldehyde resin, and resorcinol formaldehyde resin may be provided including one or more selected from the group consisting of, but not limited to.

The precipitating agent included in the non-porous polymer may be one or more selected from potassium acetate, sodium citrate, sodium chloride, ammonium chloride, sodium iodide, potassium iodide, copper sulfate and sodium thiocyanate, and the coagulant is aluminum sulfate, zinc hydroxide , at least one selected from iron hydroxide and iron chloride may be provided, but is not limited thereto.

According to an embodiment of the present invention, the photocurable resin provided with the microcapsule 110 for digestion is provided including an oligomer, a monomer, a photoinitiator and an additive. It may be cured under light conditions (UV, visible light, electron beam (EB), LED, etc.) and finally provided in the form of a film.

According to an embodiment of the present invention, the microcapsules 110 for digestion and the photocurable resin may be provided in a ratio of 1: 0.5 to 2 by weight. Preferably, the microcapsule 110 for digestion and the photocurable resin are provided in a 1: 1 weight ratio. When provided in the above range, it is possible to provide an excellent fire extinguishing effect in a range that does not impair the physical properties of the finally formed fire extinguishing film 100 . In addition, in the extinguishing film 100, the extinguishing microcapsule 110 may contain 30 to 80% by weight. Accordingly, the fire extinguishing film 100 according to the present invention can completely protect the fire extinguishing microcapsule 110 and burst the fire extinguishing microcapsule 110 all at once in a short time, enabling efficient fire suppression.

According to an embodiment of the present invention, the photocurable resin is characterized in that it contains 60 to 100 parts by weight of the monomer, 1 to 30 parts by weight of the photoinitiator, and 1 to 30 parts by weight of the additive based on 100 parts by weight of the oligomer. Accordingly, the photocurable resin is cured under light conditions, for example, UV, visible light, electron beam (EB), LED, and the like. Preferably, ultraviolet (UV) light may be provided, and in this case, it is eco-friendly as non-VOCs (Volatile Organic Compounds) because no solvent is used. In addition, the photocurable resin may be provided with a weight average molecular weight of 100 to 1,000,000.

The oligomer is a component that determines the physical properties of the cured resin and includes at least one selected from a polyacrylic resin, an epoxy resin, a urethane resin, and a silicone resin. Preferably, a polyacrylic resin may be used, and more specifically, polyacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, silicone acrylate, polyether acrylate, and the like may be used. Accordingly, it is possible to provide the effect of absorbing heat or mechanical shock of the resin, control the elasticity of the resin, and provide excellent viscosity and flowability.

The monomer is used as a diluent and can also serve as a crosslinking agent. The monomer may include at least one selected from a polyacrylic resin, an epoxy resin, a urethane resin, and a silicone resin. For example, in the case of the polyacrylic resin, polyacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, silicone acrylate, polyether acrylate, and the like may be included. For example, a polyacrylic resin may be provided, for example, methyl acrylate, ethyl acrylate, hexyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, butyl cyclohexyl acrylate, isooctyl acrylate , isononyl acrylate, isobornyl acrylate, isodecyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, cyclic trimethylol formal acrylate, phenoxy polyethylene glycol acrylic Late, lauryl acrylate, benzyl acrylate, epoxyethyl acrylate, phenoxyethyl acrylate, hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, pentaerythritol tetraacrylate, tetra Ethylene glycol diacrylate, di(trimethylolpropane) tetraacrylate, and the like may be provided.

Epoxy resins can be provided with linear polymer epoxides, for example diglycidyl ethers of polyoxyalkylene glycols, polymer epoxides with backbone epoxy groups, for example polybutadiene polyepoxy and polymer epoxides with pendant epoxy groups. For example, a glycidyl methacrylate polymer or copolymer may be provided.

The urethane resin is mainly a urethane resin obtained by including a diol component and a diisocyanate component. If necessary, a UV curable urethane resin may be provided by further including an acrylate. The diol may include an alkylene oxide-based polyol or silicone-based polyol such as polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol. For diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene 1,6-diisocyanate, isophorone diisocyanate, paratoluenesulfonyl isocyanate, dicyclomethane 4,4-diisocyanate , diphenylmethane 4,4-diisocyanate, 2,4-diisocyanate, 2,2-diisocyanate, dodecane 1,12-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate and 2-methylpenta Any one or more selected from methylene 1,5-diisocyanate may be provided.

The silicone resin is provided including polyorganosiloxane, and for example, polydimethyl siloxane resin and hydrogen silane may be provided alone or in combination.

The photoinitiator absorbs light energy to generate radical ions, cations, and the like to initiate polymerization. The photoinitiator is provided with at least one selected from an acylphosphine oxide-based compound, an α-hydroxyketone-based compound, a phenyl glyoxylate-based compound, and a benzoin ether-based compound. The photoinitiator is suitable as an initiator that can be cured using UV or LED UV lamp, for example, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (Diphenyl (2, 4,6-Trimethylbenzonyl)phosphine oxide) may be provided, but is not limited thereto.

The additive may specifically be provided with an antifoaming agent and/or a flame retardant. The antifoaming agent is added to prevent surface tension from being lowered by a third material other than air and liquid, and to remove air and air bubbles during manufacturing. In the case of a silicone-based antifoaming agent, it is prepared by emulsifying a silicone oil compound in which a fine powder inorganic filler such as silica, titanium dioxide, aluminum oxide is dispersed in silicone oil, and emulsification to improve the stability of the antifoaming agent. ), a method of dispersing the silicone oil compound by hydrophilicizing it by appropriately adjusting the amount of emulsifier used in the process can be applied.

In addition, the flame retardant is added to improve the combustion resistance, and it is possible to prevent the binder materials from lowering the extinguishing performance while burning when an excessive fire occurs, and is mainly used for safety requirements so as not to cause a larger fire. By adding an organic compound containing bromine (Br), chlorine (Cl), etc., it reacts with radicals in the combustion process to stop combustion. A halogen-based, phosphorus-based, nitrogen-based or inorganic flame retardant may be mainly used.

Halogen-based flame retardants include decabromodiphenyl oxide (DBDPO, Decabromodiphenyl oxide), decabromodiphenyl ethane (DBDPE, Decabromodiphenyl ethane), hexabromocyclododecane (HBCD, Hexabromocyclododecane), tetrabromobisphenol-A (TBBA, Tetrabromobisphenol) -A), tetrabromobisphenol A bis 2,3-dibromopropyl ether (BDDP, Tetrabromobisphenol A Bis (2,3-dibromopropyl ether), etc. may be provided, but is not limited thereto.

The phosphorus-based flame retardant may be selected from red, phosphoric acid ester-based or phosphate, phosphonate, phosphinate, phosphine oxide, and phosphazene.

Nitrogen-based flame retardants include melamine, melamine cyanurate, triphenyl isocyanurate, melamine phosphate, melamine pyrophosphate, ammonium polyphosphate, alkyl An amine phosphate (alkyl amine phosphate), piperazine acid polyphosphate (piperazine acid polyphosphate), ammonium phosphinate and the like may be provided, but is not limited thereto.

Inorganic flame retardants are metal-based inorganic oxides, such as antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate carbonate, antimony metal, antimony trichloride, antimony pentachloride, barium metaborate, zirconium oxide, zinc borate, zinc stannate, magnesium hydroxide, aluminum hydroxide, etc. may be provided, but is not limited thereto.

That is, in the present invention, the photocurable resin provided together with the fire extinguishing microcapsule 110 is provided as a film by light curing, and the shell of the fire extinguishing microcapsule contained in the film is softened by external heat, and extinguished. The extinguishing agent can be explodingly ejected from the microcapsule for digestion by the vaporization energy of the drug. Therefore, when a fire occurs, the fire can be quickly suppressed by the extinguishing agent in the microcapsule 110 for extinguishing at a specific temperature or higher.

According to an embodiment of the present invention, the film 100 including the microcapsule 110 for digestion is selected from the base layer 200, the release layer 300, and the heat insulating/insulating layer 400 on at least one surface. It is characterized by including any one or more.

Referring to FIG. 3 , it is shown that the adhesive layer 200 is laminated on one side layer of the film 100 including the microcapsule 110 for digestion. Accordingly, it can be used by attaching it to a desired adherend if necessary.

Referring to FIG. 4 , the back layer 300 is laminated on one side layer of the film 100 including the fire extinguishing microcapsule 110 . The back surface layer 300 may be included to protect the surface of the film 100 if necessary.

Referring to FIG. 5 , it is provided in a tape structure including an adhesive layer 200 and a release layer 300 on one side layer of the film 100 including the microcapsules for digestion, so that it can be utilized.

Referring to FIG. 6 , the heat insulation/insulating layer 400 may be laminated on the fire extinguishing film 100 including the fire extinguishing microcapsule 110 according to the present invention, and thus, electronic devices, communication devices, and other wires It provides insulation and insulation effects by using it in areas that need insulation, such as cables. In addition, excellent electrical resistance such as surface resistance and volume resistance are also provided.

In addition, it is not limited to the above example, and of course, it can be applied to various structures including films.

According to an embodiment of the present invention, the thickness of the film 100 including the microcapsules 110 for digestion may be provided in a range of 10 to 10,000 μm. It can be attached in a film or tape structure by adjusting the thickness as needed. That is, it can be manufactured according to the thickness and attached in the form of a film or tape to a place where there is always a fire risk such as an electric circuit breaker or a space where heat is generated inside. In addition, microcapsules for fire extinguishing in various small spaces that can be inserted in the form of films in very small spaces such as outlets, PCB boards equipped with electronic components, insulated CAPs, secondary batteries, and electronic cigarettes to extinguish fires (110) can be applied.

According to an embodiment of the present invention, the adhesive layer 200 may use a component used as an adhesive, and may use an acrylic, silicone, urethane, epoxy, natural or synthetic rubber-based component. In the case of acrylic, for example, an adhesive component including 2-ethylhexyl acrylate, butyl acrylate, vinyl acetate, acrylic acid, and the like may be used.

According to an embodiment of the present invention, the release layer 300 means a paper or film attached to the release film to protect the adhesive layer or the adhesive surface of the film, for example, polyethyl phthalate (PET), polypropylene (PP), stretched polypropylene (OPP), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), and at least one selected from polyimide (PI) is provided. Preferably, polyethyl phthalate (PET) may be provided, which is advantageous because it has low hygroscopicity, excellent heat resistance, sufficient strength and flexible properties to be bent.

According to an embodiment of the present invention, the heat insulating/insulating layer 400 may include polyimide, polyester, polyamide, polyether sulfone, mica, paper, film, and the like. The thickness is provided in a range of 10 to 5,000 μm, and it can be used in areas that require insulation, such as electronic devices, communication devices, and other wire cables, to provide insulation and insulation effect.

Referring to FIG. 6 , the heat insulation/insulating layer 400 may be laminated on the fire extinguishing film 100 including the fire extinguishing microcapsule 110 according to the present invention, and thus, electronic devices, communication devices, and other wires It provides insulation and insulation effects by using it in areas that need insulation, such as cables. In addition, excellent electrical resistance such as surface resistance and volume resistance are also provided.

In addition, it is not limited to the above example, and of course, it can be applied to various structures including films.

According to an embodiment of the present invention, the thickness of the film 100 including the microcapsules 110 for digestion may be provided in a range of 10 to 10,000 μm. It can be attached in a film or tape structure by adjusting the thickness as needed. That is, it can be manufactured according to the thickness and attached in the form of a film or tape to a place where there is always a fire risk such as an electric circuit breaker or a space where heat is generated inside. In addition, microcapsules for fire extinguishing in various small spaces that can be inserted in the form of films in very small spaces such as outlets, PCB boards equipped with electronic components, insulated CAPs, secondary batteries, and electronic cigarettes to extinguish fires (110) can be applied.

According to an embodiment of the present invention, the adhesive layer 200 may use a component used as an adhesive, and may use an acrylic, silicone, urethane, epoxy, natural or synthetic rubber-based component. In the case of acrylic, for example, an adhesive component including 2-ethylhexyl acrylate, butyl acrylate, vinyl acetate, acrylic acid, and the like may be used.

According to an embodiment of the present invention, the release layer 300 means a paper or film attached to the release film to protect the adhesive layer or the adhesive surface of the film, for example, polyethyl phthalate (PET), polypropylene (PP), stretched polypropylene (OPP), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), and at least one selected from polyimide (PI) is provided. Preferably, polyethyl phthalate (PET) may be provided, which is advantageous because it has low hygroscopicity, excellent heat resistance, sufficient strength and flexible properties to be bent.

According to an embodiment of the present invention, the heat insulating/insulating layer 400 may include polyimide, polyester, polyamide, polyether sulfone, mica, paper, film, and the like. The thickness is provided in a range of 10 to 5,000 μm, and it can be used in areas that require insulation, such as electronic devices, communication devices, and other wire cables, to provide insulation and insulation effect.

First, the microcapsule for fire extinguishing 110 polymerizes at the interface between the hydrophobic organic solvent containing the fire extinguishing agent and the aqueous surfactant to form a shell, and the shell is aged to maintain the liquidification of the fire extinguishing agent and only the shell is solidified. It is stirred to produce microcapsules, and then the microcapsules 110 are precipitated and the liquid is removed. After washing the microcapsules 110 with an aqueous solution, it is selected and dried at a low temperature. In this case, the content of the extinguishing agent is 80 to 97%.

According to an embodiment of the present invention, mixing an initiator and a monomer, preparing a photocurable resin by adding an oligomer, and an additive; preparing a photocurable resin mixture by putting the microcapsules 110 for digestion into the photocurable resin; There is provided a method of manufacturing a film 100 including a microcapsule 110 for digestion comprising; manufacturing a film by photocuring the photocurable resin mixture.

First, the initiator absorbs light energy with a photoinitiator to initiate a polymerization reaction by generating radical ions, cations, etc., and the aforementioned acylphosphine oxide-based compound, α-hydroxyketone-based compound, phenyl glyoxylate-based compound, and At least one selected from benzoin ether compounds may be provided.

The monomer serves as a diluent and a crosslinking agent, and may include at least one selected from a polyacrylic resin, an epoxy resin, a urethane resin, and a silicone resin. For example, in the case of the polyacrylic resin, polyacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, silicone acrylate, polyether acrylate, and the like may be included. Polyacrylates include methyl acrylate, ethyl acrylate, hexyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, butyl cyclohexyl acrylate, isooctyl acrylate, isononyl acrylate, isobornyl acrylate, isodecyl Acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, cyclic trimethylolformal acrylate, phenoxy polyethylene glycol acrylate, lauryl acrylate, benzyl acrylate, epoxyethyl Acrylates, phenoxyethyl acrylate, hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, pentaerythritol tetraacrylate, tetraethylene glycol diacrylate, and di(trimethylolpropane) At least one selected from tetraacrylate is provided, and it is mixed with a photoinitiator, and an antifoamer and a flame retardant are additionally added as oligomers and additives to prepare a photocurable resin.

In this case, the photocurable resin is characterized in that it contains 60 to 100 parts by weight of the monomer, 1 to 30 parts by weight of the photoinitiator, and 1 to 30 parts by weight of the additive based on 100 parts by weight of the oligomer. Now, the details are the same as those described above, and description of overlapping ranges will be omitted.

By adding the microcapsules 110 for digestion to the photocurable resin prepared as described above, a photocurable resin mixture is prepared. In particular, the photo-curable resin mixture is characterized in that the photo-curable resin: the weight ratio of the microcapsule for digestion 110 is 1: 0.5 to 2. Preferably, it may be provided in a 1:1 ratio. Accordingly, it is possible to provide an excellent fire extinguishing effect in a range that does not impair the physical properties of the finally manufactured fire extinguishing film 100 . In addition, in this case, the microcapsule 110 for fire extinguishing in the film 100 for fire extinguishing may contain 30 to 80% by weight. Accordingly, the fire extinguishing film 100 according to the present invention can completely protect the fire extinguishing microcapsule 110 and burst the fire extinguishing microcapsule 110 all at once in a short time, enabling efficient fire suppression.

According to an embodiment of the present invention, the photocuring is 100mJ/cm ² to 1,000mJ/cm ² Curing under UV conditions. Preferably, 200mJ/cm ² to 300mJ/cm ^{2 When} provided in the range, the photopolymerization initiator is decomposed and a sufficient polymerization reaction may proceed. Accordingly, the film 100 including the finally cured microcapsules 110 for digestion is provided.

The film 100 including the fire extinguishing microcapsule 110 manufactured by the above manufacturing method can be applied in a place where danger always exists or in various spaces, thereby providing an effect of preventing or quickly suppressing a fire. In particular, it can be applied to various spaces such as a very small space such as a secondary battery and an electronic cigarette. In addition, it can provide excellent ductility and heat dissipation, so it can be expected to help prevent fires.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense. Content not described here will be omitted because it can be technically inferred sufficiently by a person skilled in the art.

<Production of film containing microcapsules for digestion>

Prepare 0.5 to 1 parts by weight of initiator TPO and 4 to 5 parts by weight of PI184, 1 to 2 parts by weight of CTFA, 2 to 3 parts by weight of HDDA, 1 to 2 parts by weight of THFA, 6 to 7 parts by weight of IBOA, 7 to SR217 8 parts by weight were mixed. Here, 14 to 15 parts by weight of CN8887 as an oligomer, 9 to 10 parts by weight of PU3000, 0.1 to 0.3 parts by weight of BYK333 as an additive, and 4 to 5 parts by weight of Otsuka SPB-100 were additionally added to prepare a photocurable resin. Microcapsules for digestion were put into the photocurable resin prepared in Preparation Example 1 so that the weight ratio of the microcapsules for digestion was 1: 1, and a photocurable resin mixture was prepared. This was cured under UV 250 mJ/cm ^{2 conditions.} In this case, the curing conditions are (2600W, temperature 40°C).

[Explanation of code]

100: film containing microcapsules for digestion

110: microcapsules for digestion

111: core

112: shell

200: adhesive layer

300: release layer

400: heat insulation / insulation layer

The fire extinguishing film including the fire extinguishing microcapsule according to the present invention can be applied in a place where fire risk always exists or in various spaces, thereby providing an effect of preventing or quickly suppressing a fire. In other words, when a fire occurs, the microcapsules can be ruptured simultaneously within a short time to quickly and efficiently extinguish the fire.

In particular, it can be applied to various spaces such as places where there is always a fire risk such as outlets and electric breakers, as well as very small spaces such as rechargeable batteries and electronic cigarettes.

In addition, by providing excellent ductility and heat dissipation, it can help prevent fire.

Claims (17)

1. Contains microcapsules for digestion and photocurable resin,

   The microcapsule for digestion has a core-shell structure,

   The core contains 80 to 97% by weight of an extinguishing agent,

   The shell surrounds the core, and a film comprising microcapsules for digestion comprising a precipitant or coagulant with a non-porous polymer.
2. According to claim 1,

   The fire extinguishing microcapsule and the photocurable resin are 1: 0.5 to 2 weight ratio of the film comprising microcapsules for digestion.
3. According to claim 1,

   The extinguishing agent is fluorine carbon, fluorine chlorine carbon, fluorine bromine carbon-based halogen carbon, fluorine iodine carbon-based halogen carbon, 2-iodine-1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) ) and Iodofluorocarbon (FIC-217I1 or FIC-13I1), 1,1,1,2,2-Pentafluoroethane (CF ₃ CF ₂ H, HFC-125), 1,1,1,2,3,3,3- Heptafluoropropane (CF ₃ CHFCF ₃ ), Chlorotetrafluoroethane (CHClFCF ₃ ), fluorochemical ketone compound, dodecafluoro-2-methylpentan-3-one(FK-5-1-12, CF ₃ CF ₂ C(O)CF(CF ₃₎ ) ₂ )), 1-chloro-1,2,2,2-tetrafluoroethane (C ₂ HClF ₄ ), 2-chloro-1,1,1,2-tetrafluoroethane (CHClFCF ₃ , HCFC-124), decafluoro Cyclohexanone (perfluoro cyclohexanone), CF ₃ CF ₂ C(O)CF(CF ₃ ) ₂ (-1,1,1,2,4,4,5,5,5-nonafluoro- 2-trifluoromethyl-butan- _{3one), (CF 3} ) ₂ CFC(O)CF(CF ₃ ) ₂ (-1,1,1,2,4,5,5,5,6,6, 6,-Octafluoro-2,4,-bis(trifluoromethyl)pentan-3-one), CF ₃ CF ₂ C(O)CF ₂ CF ₂ CF ₃ , CF ₃ C(O)CF(CF ₃ ) ₂ , 1,1,1,3,3,4,4,5,5,6,6,7,7,8,8,8,-hexadodecafluorooctan-2-one (CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ C(O)CF ₃ ), 1,1,1,3,4,4,4,-heptafluoro-3-trifluoromethylbutan-2-one (CF ₃ C(O)CF(CF ₃ ) ₂ ), 1,1,1,2,4,4,5,5,-octafluoro-2-trifluoromethylpentan-3-one (HCF ₂ CF _{2 )} C(O) CF(CF ₃ ) ₂ ), 1,1,1,2,4,4,5,5,6,6,6,-undecafluoro-2-trifluoromethylhexan-3-one (CF _{3 )} CF ₂ CF ₂ C(O)CF(CF ₃ ) ₂ ), 1-Chloro-,1,1,3,4,4,4-hexafluoro-3-trifluoromethyl-butan-2-one ( (CF ₃ ) ₂ CFC(O)CF ₂ CL), 1,1,1,2,2,4,4,5,5,6,6,6-dodecafluorohexan-3-one (CF _{3 )} CF ₂ C(O)CF ₂ CF ₂ CF ₃ ), 1,1,1,5,5,5,-hexafluoropentane-2-4-dione (CF ₃ C(O)CH ₂ C(O) CF ₃ ), 1,1,1,2,5,6,6,6-octafluoro-2,5-bis (trifluoromethyl) hexane-3,4-dione ((CF ₃ ) ₂ CFC ( O)C(O)C(O)CF(CF ₃ ) ₂ ), 1,1,1,2,2,3,3,5,5,6,6,7,7,7,-tetradecafluoro Roheptan-4-one (CF ₃ CF ₂ CF ₂ C(O)CF ₂ CF ₂ CF ₃ ), 1,1,1,3,3,4,4,4-octafluorobutal-2-one ( CF ₃ C(O)CF ₂ CF ₃ ), 1,1,2,2,4,5,5,5-octafluoro-1-trifluoromethoxy-4-trifluoromethylpentan-3-one (CF ₃ OCF ₂ CF ₂ C(O)CF(CF ₃ ) ₂ ) and 1,1,1,2,4,4,5,5,6,6,7,7,7,-tridecafluoro -2-trifluoromethylheptan-3-one (CF ₃ CF ₂ CF ₂ CF ₂ C(O)CF(CF ₃ ) ₂ ) A film comprising microcapsules for digestion, characterized in that at least one selected from the group consisting of.
4. According to claim 1,

   The shell is a polyurethane resin, polyurea resin, polyamide resin, polyester resin, polycarbonate resin, aminoaldehyde resin, melamine resin, polystyrene resin, styrene-acrylate copolymer resin, styrene-methacrylate copolymer resin, A film comprising microcapsules for digestion, characterized in that at least one selected from gelatin or a derivative thereof, polyvinyl alcohol, phenol formaldehyde resin, and resorcinol formaldehyde resin.
5. According to claim 1,

   The precipitant is potassium acetate, sodium citrate, sodium chloride, ammonium chloride, sodium iodide, potassium iodide, copper sulfate, and a film comprising a microcapsule for digestion, characterized in that at least one selected from sodium thiocyanate.
6. According to claim 1,

   The coagulant is a film comprising microcapsules for digestion, characterized in that at least one selected from aluminum sulfate, zinc hydroxide, iron hydroxide and iron chloride.
7. According to claim 1,

   The photocurable resin is based on 100 parts by weight of the oligomer, 60 to 100 parts by weight of the monomer, 1 to 30 parts by weight of the photoinitiator, and 1 to 30 parts by weight of additives A film comprising microcapsules for digestion.
8. According to claim 1,

   The oligomer is a film comprising microcapsules for digestion, characterized in that it comprises at least one selected from a polyacrylic resin, an epoxy resin, a urethane resin, and a silicone resin.
9. According to claim 1,

   The monomer is a film comprising microcapsules for fire extinguishing, characterized in that it comprises at least one selected from a polyacrylic resin, an epoxy resin, a urethane resin, and a silicone resin.
10. According to claim 1,

    The photoinitiator is a film comprising microcapsules for digestion, characterized in that at least one selected from an acylphosphine oxide-based compound, an α-hydroxyketone-based compound, a phenyl glyoxylate-based compound, and a benzoin ether-based compound.
11. According to claim 1,

    The additive is a film comprising microcapsules for fire extinguishing, characterized in that it contains at least one selected from an antifoaming agent and a flame retardant.
12. According to claim 1,

    The additive is a film comprising microcapsules for fire extinguishing, characterized in that it contains at least one selected from an antifoaming agent and a flame retardant.
13. According to claim 1,

    A film comprising microcapsules for fire extinguishing, characterized in that the thickness of the fire extinguishing film is 10 to 10,000 μm.
14. preparing a photocurable resin by mixing an initiator and a monomer, and adding an oligomer and an additive;

    preparing a photocurable resin mixture by putting microcapsules for digestion into the photocurable resin; and

    Method for producing a film comprising microcapsules for digestion, comprising; manufacturing a film by photocuring the photocurable resin mixture.
15. 15. The method of claim 14,

    The photocurable resin is based on 100 parts by weight of the oligomer, 60 to 100 parts by weight of the monomer, 1 to 30 parts by weight of the photoinitiator, and 1 to 30 parts by weight of additives A method of producing a film comprising microcapsules for digestion.
16. 15. The method of claim 14,

    In the photocurable resin mixture, the weight ratio of the photocurable resin: the microcapsule for fire extinguishing is 1: 0.5 to 2.
17. 15. The method of claim 14,

    The photocuring is 100mJ/cm ² to 1,000mJ/cm ² Method for producing a film comprising microcapsules for digestion, characterized in that it proceeds.

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