KR101994813B1 - Self-extinguishing adhesive tape - Google Patents

Abstract

The present invention relates to an adhesive tape for automatic fire extinguishing, and more particularly to an adhesive tape for automatic fire extinguishing, which comprises a base film, a first fire extinguishing and adhesive layer formed on the bottom surface of the base film and including a fire extinguisher capsule and an adhesive, And a first protective release layer laminated on the bottom surface of the adhesive layer to protect the first fire-extinguishing adhesive layer, wherein the fire extinguishing capsule comprises dibromotetrafluoroethane (BrCF ₂ BrCF ₂ ), dodecafluoro-2-methylpentane (CF ₃ CF ₂ C (CF ₃ ) ₂ ), trifluoromethane (CHF ₃ ), pentafluoromethane (CHF ₂ CF ₃ ) or heptafluoropropane (CF ₃ CHFCH ₃ ) A thermoplastic resin layer formed on the outside of the extinguishing material, and an outer layer formed on the outside of the thermoplastic resin layer, wherein the outer layer comprises gelatin or polyvinyl acetate (PVA) .
According to the present invention, ignition or explosion of the battery is suppressed during abnormal heat generation due to overcharging or malfunction, and the occurrence of fire is reduced. In addition, there is an advantage that the risk of fire and explosion can be remarkably lowered simply by wrapping the outside of the lithium ion battery with the self-extinguishing tape.

Description

{Self-extinguishing adhesive tape}

The present invention relates to an adhesive tape for automatic fire extinguishing, and more particularly, to an automatic fire extinguishing tape which is applied to a lithium ion battery to reduce the internal activity of the battery during overcharge and external shock, To an adhesive tape.

BACKGROUND ART [0002] With the recent development of the information communication industry, as electronic devices have become smaller, lighter, thinner, and portable, there is a growing demand for higher energy density of batteries used as power sources for such electronic devices. Lithium secondary batteries are the ones that can best meet this demand, and researches thereon are actively being carried out.

The lithium secondary battery is manufactured by injecting a non-aqueous electrolyte containing a lithium salt and an organic solvent into an electrode structure composed of a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode. When the lithium ion is inserted and removed from the positive electrode and the negative electrode And is a secondary battery that generates electric energy by an oxidation-reduction reaction.

This lithium ion battery is currently in the spotlight due to its advantages such as high operating voltage and high energy density compared with conventional batteries such as Ni-MH battery, Ni-Cd battery, and sulfuric acid-lead battery using an electrolyte solution as an aqueous solution . However, since lithium ion batteries use organic electrolytic solutions, there is a risk of ignition and explosion, and there is a disadvantage that they are difficult to manufacture.

Therefore, the most important problem in the lithium ion battery is safety. In particular, the risk of ignition and explosion due to overcharging, penetration, heat oven, and the like is the most urgent problem to be solved.

For example, when the lithium ion battery is overcharged, the lithium ions continue to move from the anode to the cathode, and the moved lithium ions grow on the surface of the cathode to form a dendrite having a tree-like structure. These dendrites can cause overcurrent and overheating due to battery short-circuit, and in extreme cases cause explosion or fire.

In addition, when the lithium ion battery is overcharged at a rated voltage or higher, the electrolytic solution starts to decompose, and the temperature rises to reach the flash point. And by firing the case of using LiCoO _2, when the high temperature LiCoO ₂ is more, while changes to the stable structure of spinel (spinel) structure of the extra oxygen occurs, this extra oxygen moves to the electrolyte reaching the ignition point as a cathode active material Combustion or explosion will occur.

In order to prevent the heat generation due to overcharging, various methods have been proposed, such as a method of mounting a protection circuit, a method of interrupting the current using the internal pressure of the battery, and a method of adding an additive to the electrolytic solution.

However, the current interruption mechanism using the protection circuit or the internal pressure causes additional space and cost, which is against the high capacity of the battery. In addition, the method of adding an additive to the electrolytic solution has a problem that the joule heat fluctuates depending on the current value at the time of charging or the internal resistance of the battery and the operation timing of the exothermic suppression mechanism is uneven, And the like.

KR 10-0701532 B1

Accordingly, it is an object of the present invention to provide an adhesive tape for automatic fire extinguishing which prevents the risk of fire and explosion due to a battery.

It is another object of the present invention to provide an adhesive tape for automatic fire extinguishing which is capable of exerting extinguishing substances present therein at a specific temperature and exerting an excellent extinguishing function.

According to an aspect of the present invention, there is provided an automatic fire extinguishing adhesive tape comprising a base film, a first fire-extinguishing and pressure-sensitive adhesive layer formed on a bottom surface of the base film and including a fire extinguisher capsule and a pressure- And a first protective release layer laminated on the bottom surface of the fire-extinguishing pressure-sensitive adhesive layer to protect the first fire-extinguishing pressure-sensitive adhesive layer, wherein the fire extinguishing capsule comprises dibromotetrafluoroethane (BrCF ₂ BrCF ₂ ), dodecafluoro-2- pentane-3-circle _{(CF 3 CF 2 C (O} ) CF (CF 3) 2), trifluoromethanesulfonate (CHF _3), penta fluoro methane (CHF ₂ CF ₃₎ or cyclohepta fluorine propane (CF ₃ CHFCH ₃₎ A thermoplastic resin layer formed on the outside of the extinguishing material, and an outer layer formed on the outside of the thermoplastic resin layer, wherein the outer layer comprises gelatin or polyvinyl acetate (PVA) .

And an aluminum coating layer formed on the upper surface of the base film.

A second fire extinguishing agent layer including a fire extinguishing capsule formed on an upper surface of the base film and a pressure sensitive adhesive and a second protective releasing layer bonded to the upper surface of the second fire extinguishing pressure layer to protect the second fire extinguishing pressure layer, .

A base film, a fire extinguishing capsule layer formed on the top surface of the base film, the fire extinguishing capsule layer including a fire extinguishing capsule, an adhesive layer formed on the bottom surface of the base film, Wherein the extinguishing capsule comprises dibromotetrafluoroethane (BrCF ₂ BrCF ₂ ), dodecafluoro-2-methylpentane-3-one (CF ₃ CF ₂ C (O) CF (CF ₃ ) ₂ ), Pyrophoric material (CHF ₃ ), pentafluoromethane (CHF ₂ CF ₃ ) or heptafluoropropane (CF ₃ CHFCH ₃ ), a thermoplastic resin layer formed on the exterior of the extinguishing material, And an outer layer formed on the outside of the layer, wherein the outer layer includes gelatin or polyvinyl acetate (PVA).

The size of the fire extinguishing capsule is 50 to 300 μm, and the base film is any one of a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and a polyimide (PI) film.

According to the present invention, ignition or explosion of the battery is suppressed during abnormal heat generation due to overcharging or malfunction, and the occurrence of fire is reduced.

In addition, there is an advantage that the risk of fire and explosion is significantly lowered simply by wrapping the outside of the lithium ion battery with the self-extinguishing adhesive tape.

1 is a sectional view of an automatic fire extinguishing adhesive tape according to an embodiment of the present invention;
2 is a sectional view of a digestive capsule according to an embodiment of the present invention;
3 is a cross-sectional view of a state in which an aluminum coating layer is further formed on the tape of Fig.
4 is a cross-sectional view of the tape of FIG. 1 with a second fire extinguisher and a second protective release layer additionally formed;
5 is a sectional view of an adhesive tape for automatic fire extinguishing according to another embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

First, the self-extinguishing adhesive tape of the present invention can be used for a battery, especially for a lithium ion battery, and safety accidents such as fire and explosion of the battery can be alleviated by only covering the outside of the battery pack.

1, a self-extinguishing adhesive tape according to an embodiment of the present invention includes a base film 100, a base film 100 formed on the bottom surface of the base film 100, and a fire extinguishing capsule 210, A first fire extinguishing agent layer 200 including a first fire extinguishing agent layer 220 and a first protective release layer 300 bonded to the bottom surface of the first fire extinguishing agent layer 200 to protect the first fire extinguishing agent layer 200, .

The base film 100 is used as a main substrate of a tape, and can be selected in the form of transparent, black, and white, and can be selected in accordance with the application or preference. If the thickness is less than 25 占 퐉, it is difficult to use the tape as a main substrate. If the thickness is more than 75 占 퐉, the thickness of the entire tape becomes thick, .

As the base film 100, it is preferable to use any one of a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and a polyimide (PI) film.

The first fire-extinguishing adhesive layer (200) is formed on the bottom surface of the base film (100). The first fire extinguishing agent layer 200 includes the fire extinguishing capsule 210 and the adhesive 220 to enable adhesion with the battery and to extinguish the fire due to the action of the fire extinguishing capsule 210 during a fire.

2, the extinguishing capsule 210 is made of dibromotetrafluoroethane (BrCF ₂ BrCF ₂ ), dodecafluoro-2-methylpentane-3-one (CF ₃ CF ₂ C (O) The extinguishing material 211 including CF (CF ₃ ) ₂ ), trifluoromethane (CHF ₃ ), pentafluoromethane (CHF ₂ CF ₃ ) or heptafluoropropane (CF ₃ CHFCH ₃ ) A thermoplastic resin layer 212 formed on the outside of the thermoplastic resin layer 212 and an outer layer 213 formed on the outside of the thermoplastic resin layer 212.

The extinguishing medium 211 as ethane-dibromo-tetrafluoroethane (BrCF ₂ BrCF _2), dodeca-fluoro-2-methyl-pentane-3-circle _{(CF 3 CF 2 C (O} ) CF (CF 3) 2), trifluoromethanesulfonate (CHF _3), penta fluoro methane (CHF ₂ CF ₃₎ or cyclohepta fluorine propane (CF ₃ CHFCH ₃₎ may be a, such a material is cooled to absorb a lot of energy from the method have a high specific heat in case of fire flames Digest through the effect. In addition, since it expands when it receives heat, it expands in the vicinity of the flame and blocks oxygen to extinguish the fire.

The dibromotetrafluoroethane (BrCF ₂ BrCF ₂ ) is very effective for the digestion. However, the dibromotetrafluoroethane (BrCF ₂ BrCF ₂ ) Because the ozone layer is destroyed, and the diffusion property is superior to the remaining trifluoromethane, pentafluoromethane, and heptafluoropropane. That is, the dodecafluoro-2-methylpentane-3-source is transparent, colorless, almost odorless, and has an ozone depletion potential (ODP) of zero. Therefore, there is no environmental burden at all. The dodecafluoro-2-methylpentan-3-one is also excellent in electrical insulation and human stability. In general, fluorine has a very low surface tension and spreads well when it comes into contact with an object. The dodecafluoro-2-methylpentane-3-one is also a type of fluorine compound, and its surface tension is very low, so that it does not form droplets when it comes into contact with paper, but spreads quickly. This is because the intramolecular bonding force of the dodecafluoro-2-methylpentan-3-one is weak. Since the dodecafluoro-2-methylpentan-3-one is chemically very stable and does not react with other materials, and is hardly mixed with water and has a dielectric strength more than twice that of nitrogen, There is also a nature that does not go through. Since the freezing point is -108 ° C and the boiling point is 49 ° C, it exists in a liquid state at normal temperature, but when the temperature rises, it evaporates quickly and suppresses the fire. That is, the vapor pressure at room temperature is 12 times larger than that of water, and the latent heat of vaporization at room temperature is 5 times smaller than that of water. Accordingly, the dodecafluoro-2-methylpentan-3-one is easily vaporized in the event of a fire and is rapidly vaporized to extinguish the fire. The dodecafluoro-2-methylpentan-3-one is also excellent in environmental resistance, electrical insulation and human safety. Suitable.

The thermoplastic resin layer 212 surrounding the extinguishing material 211 is formed of a thermoplastic homopolymer or a copolymer and the homopolymer is formed by polymerization of one monomer and the copolymer is formed by polymerization of at least two or more monomers . For example, the thermoplastic resin layer 212 may be formed of a thermoplastic resin having a melting point of 70 to 200 ° C, and most preferably 120 to 150 ° C, so that the thermoplastic resin layer 212 can dissolve in the abnormal heat of the external environment.

The monomers used for the polymerization of the thermoplastic homopolymer or copolymer may be selected from the group consisting of ethylenic monomers, vinyl monomers and acrylic monomers, and examples thereof include propylene, 1,3-butadiene, Vinyl chloride, tetrafluoroethylene, vinyl C1-C10 alkylate (CH2CH-OC (O) R, R is C1-C10 alkyl), vinyl May be at least one of C1-C10 alkyl ether (CH2CH-OR, R is C1-C10 alkyl), vinylpyrrolidone, vinylcarbazole, acrylic acid, acrylonitrile, acrylamide and C1-C10 alkyl acrylate.

The outer layer 213 surrounding the thermoplastic resin layer 212 protects the extinguishing material 211 and the thermoplastic resin layer 212 from external impact and is formed of gelatin or polyvinyl acetate, PVA).

When the outer layer 213 is formed of the gelatin, since the gelatin is soft, it has an advantage that the extinguishing material 211 can be effectively protected from external impact. In addition, polyethylene glycol and glycerin can be further mixed in an amount of 5 to 10% by weight as an additive in 80 to 90% by weight of the gelatin, respectively, to further facilitate the formation of the gelatin layer. At this time, as the gelatin, known and commercially available industrial gelatin products can be used without limitation.

When the outer layer 213 is formed of the PVA, the PVA layer has a low melting point. Therefore, the PVA layer is easily melted when the temperature rises, and is more resistant to pressure than gelatin, so that the inner fire extinguishing material 211 can be more effectively protected from external impact have. That is, the PVA solves the weak point of the gelatin which is weak in pressure.

As described above, the fire extinguishing capsule 210 formed of the extinguishing material 211, the thermoplastic resin layer 212, and the sheath layer 213 preferably has a particle diameter of 50 to 300 μm, and the thickness of each layer is not limited.

Meanwhile, the fire extinguishing capsule 210 may be manufactured by a general microcapsule manufacturing method. Typically, the microcapsule is produced by post-treating the polymer. This is a method in which the water-insoluble polymer, the organic solvent, and the substances to be contained in the microcapsule are mixed together, and the mixture is homogeneously mixed by thorough stirring, followed by removing the organic solvent. In addition to this, a method of removing the aqueous dispersion by heating or vacuum, a method of preparing the material for forming the outer wall of the microcapsule through interfacial polymerization, a method of incorporating 1 to 30 parts by weight of a heterogeneous polymer into the inside thereof, Any of various methods used for producing microcapsules can be applied.

More specifically, for the production of a capsule, it includes a monomer, a digesting agent, a dispersant, a surfactant and an initiator. For example, monomers of AN (acrylonitrile), digesting substances, polyvinyl alcohol (PVA), surfactant SDS (sodium dodecyl sulfate), and initiator AIBN (azobisisobutylnitrile). That is, first, 1 g of PVA is added to 50 ml of water to prepare a dispersion, 40 ml of digestion material and 0.4 g of SDS are added to 100 ml of water, and a digestion composition solution is prepared. Then, the dispersion prepared in this digestion composition solution is added and stirred in the reactor for about 2 hours to prepare a dispersed mixture. Next, a monomer solution containing 10 ml of AN in 10 ml of water is added to the dispersed mixture, and further stirred at 2000 rpm for 1 hour. Then, 5 g of AIBN is added and reacted in a thermostatic chamber at 60 ° C for 48 hours to prepare microcapsules.

Also, the method of forming the outer layer 213 containing gelatin or PVA on the outside is also well known in the art. Since encapsulation of gelatin or the method of forming the outer cover with synthetic resin is well known, Is omitted.

That is, in the digestive capsule 210 of the present invention, the extinguishing material 211 is protected from external impact by the external layer 213, and when the temperature rises by 120 ° C or more, the external layer 213 and the thermoplastic resin layer 212 react and are broken Since the internal extinguishing material 211 is ejected by the firebox, the cooling and oxygen-blocking effect is exhibited.

If the outer layer is formed only by the outer layer 213, the outer layer 213 is easily broken at a low temperature. If the outer layer is formed only by the thermoplastic resin layer 212, 210 are not suitable for self-extinguishing because they are broken. In the present invention, these disadvantages are solved through the outer skin layer 213 and the outer surface of the thermoplastic resin layer 212.

The adhesive 220 for forming the first fire extinguishing adhesive layer 200 together with the fire extinguishing capsule 210 is not limited in its kind and may be any of various types applied in the field of tapes. Illustratively, it may be a product composed of an acrylic copolymer and a curing agent, and is composed of 98 to 99.9% by weight of an acrylic copolymer and 0.1 to 2% by weight of a curing agent. As the curing agent, isocyanate, epoxy, aziridine and the like can be used.

In addition, the first fire extinguishing agent layer 200 may have a weight ratio of the pressure-sensitive adhesive 220 to the fire extinguishing capsule 210 of about 1: 0.1 to 2.

A protective release layer 300 for protecting the bottom of the first fire-extinguishing and pressure-sensitive adhesive layer 200 is formed on the bottom of the first fire-extinguishing and pressure-sensitive adhesive layer 200. The protective release layer 300 may be made of various materials known in the art. For example, a PET film or a product in which a paper is coated with silicone may be used, and its thickness is not limited.

The automatic fire extinguishing tape constructed as described above can be easily applied to a battery to lower the risk of fire and explosion and to easily extinguish the fire.

In the manufacture of the self-extinguishing tape, a mixture of the digestive capsules 210 and the adhesive 220 is coated on the base film 100. At this time, the coating thickness may be 60 to 300 mu m.

Then, it is dried at 70 to 90 ° C. for 1 to 10 minutes, followed by laminating the protective release layer 300 with a pressure of 2 to 4 kgf / cm 2 and aging at room temperature for 40 to 50 hours.

3, an aluminum coating layer 400 formed on the upper surface of the base film 100 may be further included. The aluminum coating layer 400 is for the purpose of label printing or silver color. The aluminum coating layer 400 may be formed by mixing an aluminum paste and one of polyurethane, polyester, and epoxy resin in an amount of 1 to 2 mu m Thickness. Here, one kind of the aluminum paste, polyurethane, polyester, and epoxy resin may be mixed at a weight ratio of 1: 1 to 2, and any of commercially available products may be used.

As shown in FIG. 4, the tape may be applied as a double-sided tape instead of a single-sided tape. The tape includes a fire extinguishing capsule 210 'and a pressure-sensitive adhesive 220' And a second protective release layer 300 'that is laminated on the upper surface of the second fire extinguishing agent layer 200' and protects the second fire extinguishing agent layer 200 ' .

Since the second fire extinguishing agent layer 200 'and the second protective mold release layer 300' are the same as the first fire extinguishing adhesive layer 200 and the first protective mold release layer 300, detailed description thereof will be omitted . However, the first fire extinguishing adhesive layer (200) is coated on one surface of the base film (100), and the first protective release layer (300) is joined to the base film Coating the second fire extinguishing pressure-sensitive adhesive layer 200 ', and laminating the second protective release layer 300'.

5, the fire extinguishing capsule layer 200a is formed on the upper surface of the base film 100, and the fire extinguishing capsule layer 200a is formed on the bottom surface of the base film 100, The adhesive layer 200b can be formed. A protective release layer 300a is laminated on the bottom surface of the adhesive layer 200b.

At this time, the extinguishing capsule layer 200a contains 30.0 to 70.0% by weight of one kind of resin selected from the group consisting of epoxy, polyurethane, polyester, rubber, acrylic, silicone and amine, isocyanate, epoxy, aziridine, amine and amidazole 0.1 to 2.0% by weight of one type of curing agent, and 29.9 to 68% by weight of the digestive capsule 210 are directly coated on the base film 100, dried at 60 to 80 ° C for 2 to 6 minutes, And aged for 40 to 60 hours. At this time, the kind of the resin and the curing agent is not specified, and various resins and curing agents known in the art can be used. The thickness is preferably from 50 to 350 mu m, but this is not necessarily limitative.

The adhesive layer 200a is prepared by mixing 98 to 99.9% by weight of an acrylic copolymer with 0.1 to 2.0% by weight of one kind of curing agent selected from the group consisting of isocyanate, epoxy and aziridine. After coating the protective release layer 300a with 1 Dried at 80 to 130 ° C. for 5 minutes and then lapped on the base film 100 at a pressure of 1 to 5 kgf / cm 2 and aged at a temperature of 45 to 55 ° C. for 40 to 60 hours.

As described above, the automatic fire extinguishing tape having the above-described structure is advantageous in that it exerts an excellent self extinguishing effect only by wrapping the outer surface of the battery.

While the present invention has been described with reference to the above-described embodiments and accompanying drawings, it is to be understood that the invention may be embodied in many different forms without departing from the spirit or scope of the invention. Accordingly, the scope of the present invention is defined by the appended claims and their equivalents, and is not limited by the specific embodiments described herein.

100: substrate film
200: first fire-extinguishing pressure-sensitive adhesive layer 200 ': second fire-
200a: fire-extinguishing capsule layer 200b: adhesive layer
210: digestive capsule 220: adhesive
211: extinguishing material 212: thermoplastic resin layer
213:
300: first protective release layer 300 ': second protective release layer
300a: protective release layer 400: aluminum coating layer

Claims (5)

A base film (film) 100,
A first fire extinguishing adhesive layer 200 formed on the bottom surface of the base film 100 and including a fire extinguisher capsule 210 and an adhesive 220,
A first protective release layer 300 laminated on the bottom surface of the first fire-extinguishing pressure-sensitive adhesive layer 200 to protect the first fire-extinguishing pressure-sensitive adhesive layer 200,
And an aluminum coating layer (400) formed on an upper surface of the base film (100)
The digestive capsule 210 as ethane-dibromo-tetrafluoroethane (BrCF ₂ BrCF _2), dodeca-fluoro-2-methyl-pentane-3-circle _{(CF 3 CF 2 C (O} ) CF (CF 3) 2), The extinguishing material 211 containing trifluoromethane (CHF ₃ ), pentafluoromethane (CHF ₂ CF ₃ ) or heptafluoropropane (CF ₃ CHFCH ₃ ), the melting point formed at the outside of the extinguishing material 211 is 120 A thermoplastic resin layer 212 having a thickness of about 150 DEG C and an outer layer 213 formed outside the thermoplastic resin layer 212,
The outer layer 213 includes polyvinyl acetate (PVA)
The size of the fire extinguishing capsule 210 is 50 to 300 탆,
Wherein the base film (100) is one of a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and a polyimide (PI) film. delete delete delete delete

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