High heat-resistant resin composition for local fire extinguishing

Abstract

The present invention relates to a high heat-resistant resin composition for local fire extinguishing and a high heat-resistant binder for local fire extinguishing and, more particularly, to a high heat-resistant resin composition for local fire extinguishing and a high heat-resistant binder for local fire extinguishing, in which, when a fire occurs, not all fire-extinguishing agents in the composition are exhausted, but only fire-extinguishing agents at an area where the fire has occurred perform a fire-extinguishing action, enabling a sustained response to ongoing fires and, at the same time, enabling efficient and excellent fire-extinguishing performance.

Description

High-heat resistant resin composition for local fire extinguishing

[0001] The present invention relates to a high-heat-resistant resin composition for local fire extinguishing and a high-heat-resistant binder for local fire extinguishing. More specifically, the invention relates to a high-heat-resistant resin composition for local fire extinguishing that, in the event of a fire, allows only the extinguishing agent in the area where the fire occurred to perform the extinguishing action, rather than the entire extinguishing agent in the composition being depleted, thereby enabling response to continuously occurring fires and simultaneously providing efficient and excellent extinguishing action.

[0002]

[0003] In the current era where the widespread adoption of electrical appliances has become commonplace, while these products provide convenience, they simultaneously cast a shadow over our daily lives with the risk of fire caused by malfunctions or aging. Since the timing of fires caused by electrical appliances is difficult to predict, they occur frequently and are difficult to suppress from the outside, it is more desirable to prevent fires from occurring in the first place and to extinguish them in their very early stages, rather than trying to suppress them after they have already happened.

[0004]

[0005] Accordingly, preventive measures to preemptively prevent fires have been reported in the past; these methods involved equipping specific equipment with fire extinguishing agents that activate to suppress the fire upon occurrence. While these methods may be advantageous in that they can extinguish large fires, the equipped extinguishing agents are completely depleted after a single action, often leaving the system unable to respond to subsequent fires that occur sequentially. In particular, fires caused by electronic devices frequently occur continuously, making it extremely difficult to respond to such situations using conventional fire extinguishing methods.

[0006]

[0007] These problems have been particularly pronounced in the electric vehicle market, where the scale of the industry has increased explosively in recent years. In the case of electric vehicle batteries, multiple cells are assembled to form a single module, and multiple modules are assembled to form a battery. The cells within a module independently constitute individual batteries, and each battery independently carries a risk of fire. However, if thermal runaway occurs in a single cell, other cells within the same module may enter a fire risk stage due to the influence of such environmental changes. Furthermore, since short circuits are related to the charging and discharging method, cells within a shared module may be in a similar state regarding the occurrence of a short circuit. This implies that if a fire occurs in one cell within a module, fires may sequentially occur in other cells as well. Consequently, there was a problem in that if conventional fire extinguishing means were provided, all internal extinguishing means could be exhausted when a fire occurred in a single cell, leaving the system defenseless against secondary and tertiary fires.

[0008]

[0009] As such, the widespread adoption of electric products, such as electric vehicles, has brought about the risk of sequential and continuous fires. Therefore, to address this problem, there is an urgent need to develop fire extinguishing compositions that can respond to continuous and sequential fires while simultaneously exhibiting high extinguishing power and enabling the efficient operation of fire extinguishing means.

[0010]

[0011] [Prior Art Literature]

[0012] [Patent Literature]

[0013] (Patent Document 1) Patent Publication No. 10-1212022

[0014]

[0015] The present invention is provided to solve the aforementioned problem, and aims to provide a high-heat-resistant resin composition for local fire extinguishing that, in the event of a fire, allows only the extinguishing agent in the area where the fire occurred to perform the extinguishing action rather than the entire extinguishing agent in the composition being depleted, thereby enabling response to continuously occurring fires and simultaneously providing efficient and excellent extinguishing action.

[0016]

[0017] To solve the above-mentioned problem, the present invention provides a high heat-resistant resin composition for local fire extinguishing comprising: a binder comprising a siloxane-based resin comprising repeating units of the following chemical formula 1; and a fire extinguishing agent powder dispersed within the binder.

[0018] <Chemical Formula 1>

[0019]

[0020] (In this case, R1 and R2 are each independently an alkyl group having 1 to 10 carbon atoms.)

[0021] In addition, the above siloxane-based resin may have a TGA (d50%) value of 350 to 600°C.

[0022] In addition, the above siloxane-based resin may be formed through a hydrosilylation reaction.

[0023] In addition, the above high-heat-resistant resin composition for local fire extinguishing may further include a dispersant.

[0024] In addition, the above high-heat-resistant resin composition for local fire extinguishing may further include a heat-resistant filler.

[0025] In addition, the heat-resistant filler may be a hollow filler.

[0026] In addition, the fire extinguishing agent powder may include an alkali salt that generates alkali radicals by thermal energy, a chlorate, and a fire extinguishing aid that generates thermal energy by burning together with the chlorate.

[0027] In addition, the average diameter of the fire extinguishing agent powder may be 1 to 200 μm.

[0028] In addition, to solve the above-mentioned problem, the present invention provides a two-component high-heat-resistant resin composition for local fire extinguishing comprising: a first liquid comprising vinyl siloxane; and a second liquid comprising hydrogen siloxane; wherein at least one of the first liquid and the second liquid further comprises fire extinguishing agent powder.

[0029] In addition, the first liquid comprises a first vinyl siloxane and a second vinyl siloxane, wherein the first vinyl siloxane has a viscosity of 50 or more and less than 200 cps and a Si-Vi content of 0.2 or more and less than 0.5 mmol / g, and the second vinyl siloxane has a viscosity of 200 or more and less than 1500 cps and a Si-Vi content of 0.05 or more and less than 0.2 mmol / g.

[0030] In addition, the second liquid may include a two-sided and side-chain hydrogen siloxane and a side-chain hydrogen siloxane.

[0031]

[0032] In addition, at least one of the first liquid and the second liquid may further include a heat-resistant filler.

[0033] In addition, to solve the above-mentioned problem, the present invention provides a battery module having a fire extinguishing layer formed thereon, comprising: one or more battery cells; a casing that accommodates the plurality of battery cells; and a fire extinguishing layer in which a high heat-resistant resin composition for local fire extinguishing according to any one of claims 1 to 17 is applied to the inner surface of the casing facing the battery cells, which faces the leakage risk area of ​​the battery cells.

[0034] Additionally, the battery cell comprises: an electrode; a pouch that forms a pocket in which the electrode and electrolyte are received, surrounds the electrode to protect it from the outside, and includes a first outer layer forming a first surface of the pocket and a second outer layer forming a second surface of the pocket, wherein the first outer layer and the second outer layer are integrally formed and are folded and overlapped to form a sealing portion joined together at the outer edge of the pocket; and a lead tab extending from the electrode to the outside of the pouch; wherein the sealing portion includes a pair of short sides on the side where the lead tab is located and a pair of long sides that are orthogonal to the short sides and longer than the short sides, wherein the leakage risk area is the central region of the side facing the folding side among the long sides, and is disposed in the space between the lead tabs of mutually adjacent battery cells among the plurality of battery cells, and may further include a heat transfer prevention unit comprising a high heat-resistant resin composition for local fire suppression according to any one of claims 1 to 17.

[0035]

[0036] In the expressions “substituted or unsubstituted” as used herein, “substitution” means that one or more hydrogen atoms in a hydrocarbon are each, independently of one another, replaced by the same or different substituents. Useful substituents include, but are not limited to, the following.

[0037] These substituents include -F; -Cl; -Br; -CN; -NO2; -OH; an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, or -OH; an alkoxy group having 1 to 20 carbon atoms substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, or -OH; an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, or -OH; an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a heteroaryl group having 6 to 30 carbon atoms substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, or -OH; It may be one or more selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, or -OH; an alkyl group having 1 to 20 carbon atoms, a C1 to C20 alkoxy group, a heterocycloalkyl group having 5 to 30 carbon atoms substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, or -OH; and a group represented by -N(G1)(G2). In this case, G1 and G2 may each independently be hydrogen; an alkyl group having 1 to 10 carbon atoms; or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms.

[0038] The term “aryl group” as used in this specification refers to a polyunsaturated, aromatic, hydrocarbon substituent that may be a single ring or a multi-ring fused or covalently bonded together. Additionally, an aryl group having n carbon atoms refers to an aryl group in which the hydrocarbon ring forming the heavy chain of the aryl group has n carbon atoms, and this may be substituted or unsubstituted.

[0039] In this specification, “heteroaryl group” means an aryl group (or ring) comprising 1 to 4 heteroatoms selected from nitrogen (N), oxygen (O), and sulfur (S) (in each separate ring in the case of multiple rings), wherein the nitrogen and sulfur atoms are oxidized in some cases, and the nitrogen atom(s) are quaternized in some cases. The heteroaryl group may be bonded to the rest of the molecule through carbons or heteroatoms. Additionally, a heteroaryl group having n carbon atoms means a heteroaryl group in which the number of carbons in the hydrocarbon ring of the heavy chain of the heteroaryl group is n, which may be substituted or unsubstituted.

[0040] In this specification, the term “alkyl group” is understood to mean a straight-chain, branched-chain, or cyclic hydrocarbon group having 1 to 20 carbon atoms, particularly generally. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. An alkyl group having n carbon atoms means an alkyl group in which the number of carbon atoms in the hydrocarbon chain of the heavy chain of the said alkyl group is n, which may be substituted or unsubstituted.

[0041] In this specification, unless otherwise defined, an alkylene group is a divalent atomic group formed by excluding one hydrogen atom of the "alkyl group," and may have a saturated or unsaturated form.

[0042] In this specification, unless otherwise defined, the term "arylene group" may mean a divalent atomic group formed by excluding one hydrogen atom from the "aryl group."

[0043]

[0044] According to the present invention, when a fire occurs, not all fire extinguishing agents within the composition are consumed, but only the fire extinguishing agent in the area where the fire occurred performs the extinguishing action, thereby enabling response to continuously occurring fires and, at the same time, providing a high-heat-resistant resin composition for local fire extinguishing that can perform an efficient and excellent extinguishing action.

[0045]

[0046] Figure 1 shows a graph of TGA measured in Examples 1 to 3.

[0047] Figure 2 shows a photograph of a torch evaluation performed on Example 1.

[0048] Figure 3 shows a photograph of the torch evaluation performed on Comparative Example 1.

[0049] Figure 4 shows a photograph of the torch evaluation performed for Example 1.

[0050] Figure 5 shows a photograph of the torch evaluation performed on Comparative Example 1.

[0051] Figure 6 shows a photograph of an evaluation chamber for battery penetration evaluation.

[0052] Figure 7 shows the process and result photos of the battery penetration evaluation performed for Example 1.

[0053] Figure 8 shows a photograph of an evaluation chamber and case for battery heating evaluation.

[0054] Figure 9 shows the process and result photos of the battery heating evaluation performed for Example 1.

[0055] Figure 10 shows the process and result photos of the battery heating evaluation performed for Comparative Example 1.

[0056] Figure 11 is a drawing illustrating a typical pouch-type battery cell.

[0057] FIG. 12 is a plan view and a cross-sectional view of the pouch-type battery cell of FIG. 1.

[0058] FIG. 13 is a drawing illustrating a battery module having pouch-type cells arranged according to a preferred embodiment of the present invention.

[0059] FIG. 14 is a drawing illustrating a battery module having pouch-type cells arranged according to a preferred embodiment of the present invention.

[0060] FIG. 15 is a drawing illustrating the pattern of a fire extinguishing layer of a battery module according to preferred embodiments of the present invention.

[0061] FIG. 16 is a drawing illustrating a heat transfer prevention unit disposed in a battery module according to preferred embodiments of the present invention.

[0062]

[0063] Embodiments of the present invention are described below in detail so that those skilled in the art can easily implement them. The present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0064]

[0065] In this specification, "for local fire suppression" may mean a use for suppressing local fires. More specifically, "local fire suppression action" means a fire suppression action in which, when a fire occurs in a location adjacent to a composition containing a fire suppression agent, only the fire suppression agent near the part of the composition where the fire occurred performs the fire suppression action to suppress the fire, and the fire suppression agent in the part of the composition where no fire occurred does not participate in the reaction.

[0066]

[0067] As described above, conventional fire extinguishing means designed to prevent fires have been unable to respond effectively to continuous and sequential fires because they perform extinguishing operations sequentially and all at once when a fire occurs. This has failed to resolve the everyday risk of fire, particularly in the modern era where the widespread adoption of electronic products such as electric vehicles has become commonplace.

[0068] Accordingly, the present invention solves the aforementioned problem by providing a high-heat-resistant resin composition for local fire extinguishing comprising a binder containing a siloxane-based resin containing repeating units of Chemical Formula 1 below; and a fire extinguishing agent powder dispersed within the binder. As a result, when a fire occurs, not all fire extinguishing agents in the composition are consumed, but only the fire extinguishing agent in the area where the fire occurred performs the extinguishing action, thereby enabling response to continuously occurring fires and, at the same time, providing a high-heat-resistant resin composition for local fire extinguishing capable of efficient and excellent extinguishing action.

[0069]

[0070] <Chemical Formula 1>

[0071]

[0072] (In this case, R1 and R2 are each independently an alkyl group having 1 to 10 carbon atoms.)

[0073]

[0074] More specifically, the high-heat-resistant resin composition for local fire extinguishing according to the present invention has a fire extinguishing agent powder dispersed within a binder containing the siloxane-based resin.

[0075] The aforementioned fire extinguishing agent powder triggers a extinguishing reaction and performs a fire extinguishing action when it reaches a specific temperature due to the occurrence of a fire. In this case, according to conventional fire extinguishing methods, when a fire occurs, not only the portion of the extinguishing agent necessary for extinguishing the fire near the source of the fire but also the extinguishing agent located far from the source of the fire participates in a chain reaction. This is because the extinguishing agent located at a distance reacts due to the heat generated by the fire, or adjacent extinguishing agents participate in the reaction due to the heat generated during the extinguishing process.

[0076] Accordingly, the present invention solves the above problem by dispersing fire extinguishing agent powder within a binder containing a siloxane-based resin. Since the fire extinguishing agent powder is dispersed within a binder containing a siloxane-based resin, the fire extinguishing agent located far from the fire does not reach a temperature at which a extinguishing reaction is possible due to the high heat resistance of the resin. Consequently, only the amount of fire extinguishing agent necessary for fire suppression in the area where the fire occurred performs the extinguishing action, thereby enabling localized extinguishing action. In conclusion, it becomes possible to respond to continuously occurring fires and also enables efficient extinguishing action.

[0077] More specifically, as the siloxane-based resin containing the repeating unit of Chemical Formula 1 as in the present invention has excellent heat resistance and is also effective in preventing excess digestion reactions unrelated to digestion action, when using the siloxane-based resin, it can be very effective in local digestion action.

[0078]

[0079] More specifically, R1 and R2 are each independently alkyl groups having 1 to 10 carbon atoms, and may be one or more selected from the group consisting of, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, and neopentyl group.

[0080]

[0081] More specifically, the siloxane-based resin may have a TGA (d50%) value of 350 to 600°C, and more preferably, a TGA (d50%) value of 420 to 550°C. In this case, if the TGA (d50%) value of the siloxane-based resin is less than 350°C, the high heat resistance of the siloxane-based resin is not secured, which may lead to a problem where excess extinguishing reaction occurs in areas other than those necessary for fire suppression when a fire occurs. In addition, if the TGA (d50%) value of the siloxane-based resin exceeds 600°C, the extinguishing agent may not properly participate in the reaction due to the excessively high heat resistance value, resulting in a decrease in extinguishing efficiency. However, if the TGA (d50%) value is within the range of 420°C to 550°C, the localized extinguishing efficiency may be best, where the extinguishing agent reacts only in the area where the fire occurred while maintaining extinguishing performance.

[0082]

[0083] More specifically, the above siloxane-based resin may be formed through a hydrosilylation reaction.

[0084] More specifically, a hydrosilylation reaction is a reaction between an unsaturated bond, such as a double or triple bond, and a silicon-hydrogen bond, in which a bond is formed between the element forming the double or triple bond and silicon. The hydrosilylation reaction may be, for example, a reaction between a carbon-carbon double bond and a Si-H bond, as shown in Reaction Scheme 1 below.

[0085] <Reaction Equation 1>

[0086]

[0087]

[0088] More specifically, the siloxane resin may include double or triple bonds for a hydrosilylation reaction, and simultaneously include Si-H bonds. In this case, the double or triple bonds may be included in functional groups such as alkyl groups, heteroalkyl groups, aryl groups, or heteroaryl groups bonded to silicon, or may be included in the siloxane resin by adding an additive having double or triple bonds.

[0089] More specifically, the type of additive having a double or triple bond is not particularly limited, but may be one or more selected from the group consisting of substituted or unsubstituted alkanes, alkenes, alkynes, cycloalkanes, cycloalkenes, cycloalkynes, aryls, and derivatives having 2 to 10 carbon atoms.

[0090] As described above, when a siloxane-based resin is formed by a hydrosilylation reaction, the silicon is bonded to surrounding double or triple bonds, thereby forming a more complex three-dimensional network structure. Accordingly, the high heat resistance of the resin can be improved, and consequently, the local fire extinguishing ability of the local fire extinguishing resin composition according to the present invention can be improved.

[0091]

[0092] More specifically, the binder may be a siloxane-based resin further comprising a repeating unit of the following chemical formula 2.

[0093] <Chemical Formula 2>

[0094]

[0095]

[0096] (wherein, R3 and R4 are each independently selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an aryl group having 3 to 10 carbon atoms, and a heteroaryl group having 1 to 10 carbon atoms, and

[0097] At least one of the above R3 and R4 is an aryl group having 3 to 10 carbon atoms or a heteroaryl group having 1 to 10 carbon atoms.

[0098]

[0099] More specifically, when the binder comprises a siloxane-based resin that further comprises a repeating unit of Formula 2 as described above, it comprises a repeating unit comprising at least one aryl group or a heteroaryl group. In this case, when the siloxane-based resin comprises an aryl group or a heteroaryl group, its heat resistance may be further improved, and accordingly, the local fire extinguishing ability of the local fire extinguishing resin composition according to the present invention may be improved.

[0100] More specifically, at least one of the above R3 and R4 may be an aryl group having 3 to 10 carbon atoms or a heteroaryl group having 1 to 10 carbon atoms, and the aryl group or heteroaryl group may be one or more selected from the group consisting of, for example, a phenyl group, a benzyl group, anthryl group, a naphthyl group, or a phenanthryl group.

[0101]

[0102] More specifically, the binder may be a siloxane-based resin further comprising repeating units of the following chemical formulas 3 and 4, wherein the double or triple bond included in the following chemical formula 3 and the hydrogen siloxane included in the following chemical formula 4 are combined by a hydrosilylation reaction, so that the binder can form a three-dimensional network structure.

[0103] <Chemical Formula 3>

[0104]

[0105]

[0106] (wherein, R5 and R6 are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 3 to 10 carbon atoms, and a heteroaryl group having 1 to 10 carbon atoms, and

[0107] At least one of the above R5 and R6 includes a double bond or a triple bond.)

[0108] <Chemical Formula 4>

[0109]

[0110]

[0111] (wherein, R7 and R8 are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 3 to 10 carbon atoms, and a heteroaryl group having 1 to 10 carbon atoms, and

[0112] At least one of the above R7 and R8 is hydrogen.)

[0113]

[0114] More specifically, when the binder comprises repeating units of Formula 3 and Formula 4, and the hydrogel siloxane included in Formula 4 and the double or triple bond included in Formula 3 are bonded by a hydrosilylation reaction, the siloxane-based resin has a linear structure and, as the repeating units included in various chains are bonded, it has a network structure, and accordingly, the heat resistance of the resin is improved, and as a result, excellent extinguishing ability, which is locally lacking, can be secured.

[0115]

[0116] More specifically, one or more of the above R5 and R6 may be vinyl groups. When one or more of the above R5 and R6 are vinyl groups, the hydrogen siloxane contained in the repeating unit of the above chemical formula 4 undergoes a hydrosilylation reaction with these vinyl groups, so that the repeating unit of the above chemical formula 3 and the repeating unit of the above chemical formula 4 can be bonded very closely, thereby forming a very dense structure. Consequently, heat resistance can be improved compared to the case where one or more of the above R5 and R6 do not have vinyl groups, and accordingly, the local fire extinguishing performance of the high heat-resistant resin composition for local fire extinguishing according to the present invention can be improved.

[0117]

[0118] More specifically, the binder is a siloxane-based resin further comprising a repeating unit of the following chemical formula 5, and when X1 or X2 included in the following chemical formula 5 is oxygen, the X1 or X2 may be combined with silicon of another repeating unit so that the binder forms a three-dimensional network structure.

[0119] <Chemical Formula 5>

[0120]

[0121]

[0122] (wherein, X1 and X2 are each independently selected from the group consisting of hydrogen, oxygen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 3 to 10 carbon atoms, and a heteroaryl group having 1 to 10 carbon atoms, and

[0123] At least one of the above X1 and X2 is oxygen.)

[0124]

[0125] More specifically, when the binder comprises a siloxane-based resin that further comprises repeating units of Chemical Formula 5, the heat resistance of the resin may be improved as the siloxane-based resin may have a network structure rather than a linear structure, and consequently, the local fire extinguishing performance of the local fire extinguishing resin composition according to the present invention may be improved.

[0126]

[0127] In particular, the repeating units of chemical formulas 2 to 5 may be appropriately included so that the TGA (d50%) value of the siloxane resin is adjusted to within 350°C to 600°C, preferably 420°C to 550°C.

[0128]

[0129] More specifically, the binder may be a siloxane-based resin comprising repeating units of the following chemical formulas 1 to 5.

[0130] <Chemical Formula 1>

[0131]

[0132]

[0133] <Chemical Formula 2>

[0134]

[0135]

[0136] <Chemical Formula 3>

[0137]

[0138]

[0139] <Chemical Formula 4>

[0140]

[0141]

[0142] <Chemical Formula 5>

[0143]

[0144]

[0145] More specifically, when the binder comprises all of the repeating units of Chemical Formulas 1 to 5, the high heat resistance of the binder is ensured, and thus the local fire extinguishing performance of the high heat-resistant resin composition for local fire extinguishing according to the present invention can be improved.

[0146]

[0147] More specifically, for 1 mole of the repeating unit of the above chemical formula 1, the repeating unit of the above chemical formula 2 may be included in an amount of 0.01 to 0.5 moles, the repeating unit of the above chemical formula 3 in an amount of 0.01 to 0.5 moles, the repeating unit of the above chemical formula 4 in an amount of 0.01 to 0.5 moles, and the repeating unit of the above chemical formula 5 in an amount of 0.01 to 0.5 moles.

[0148]

[0149] More specifically, the binder may be in the form of a mixture of a solid and a solvent, and the solid may include the repeating unit described above.

[0150] More specifically, the solvent may be a solvent constituting a siloxane-based resin, and is not particularly limited, but may be an alcohol or kerone solvent, and for example, may be any one selected from the group consisting of methanol, ethanol, isopropanol, butanol, benzyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol.

[0151] More specifically, the solid content of the binder may be included in an amount of 10 to 95 parts by weight per 100 parts by weight of the total binder.

[0152]

[0153] More specifically, the binder may be included in an amount of 10 to 70 parts by weight in 100 parts by weight of the high heat-resistant resin composition for local fire extinguishing.

[0154]

[0155] More specifically, the type of the fire extinguishing agent powder is not particularly limited and commonly used fire extinguishing agent powder may be used, but preferably, it may include an alkali salt that generates alkali radicals by thermal energy, a chlorate, and a fire extinguishing aid that generates thermal energy by burning together with the chlorate.

[0156] While various types of fire extinguishing agents exist, in the case of agents utilizing alkali salts, alkali radicals are formed during the extinguishing process. These radicals extinguish the fire by blocking the alkali chain reaction that occurs during the fire. Therefore, alkali salts can effectively block the extinguishing process even with a small amount of the agent.

[0157] More specifically, when a fire occurs, the combustible material that caused the fire receives thermal energy and forms radicals, and as these radicals generate a chain reaction with oxygen in the air, the radicals propagate and the fire reaction continues. At this time, in the case of the fire extinguishing agent using the alkali salt, alkali radicals are formed by the thermal energy generated during the fire, and these alkali radicals react with the radicals that are formed and propagated in a chain reaction during the fire reaction, converting them into compounds other than radicals and terminating the radical chain reaction, thereby performing a fire extinguishing action.

[0158] Accordingly, when a fire extinguishing agent powder containing the alkali salt is dispersed in a high-heat-resistant siloxane-based resin according to the present invention, the alkali salt can form alkali radicals only near the area where the fire occurred, and the fire caused by the reaction of the formed alkali radicals can be effectively blocked. In this way, the fire extinguishing action utilizing a radical chain reaction can be particularly excellent in the high-heat-resistant resin composition for local fire extinguishing according to the present invention.

[0159] In particular, in the case of fire extinguishing agents utilizing alkali radical reactions, additional substances are often added to induce the reaction of alkali radicals. Furthermore, since heat is generated during the reaction process, once a fire extinguishing reaction is induced, all surrounding extinguishing agents react, resulting in a problem where only a single extinguishing action is possible. This presented a problem in that it could not prevent secondary and tertiary fires, particularly in cases such as batteries where each cell is separated and poses a fire risk. Accordingly, in the case of the present invention, even when using a fire extinguishing agent utilizing such an alkali radical reaction, it is possible to effectively prevent extinguishing agents that are not necessary for fire suppression from participating in the reaction in areas other than where the fire occurred. Consequently, a localized and efficient fire extinguishing reaction is possible, and continuous fires can be prevented.

[0160]

[0161] More specifically, the alkali salt may be a sodium salt and / or a potassium salt. In this case, the alkali salt may include one or more selected from the group consisting of citric acid, ethylenediamine, acetic acid, phthalic acid, oxalic acid, potassium bicarbonate, and propionic acid, and for example, may be at least one selected from the group consisting of potassium acetate, potassium propionate, monopotassium citrate, disodium citrate, tripotassium citrate, potassium tetrahydrogen ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, potassium tetrahydrogen ethylenediamine tetraacetic acid, potassium hydrogen phthalate, disodium phthalate, potassium hydrogen oxalate, disodium oxalate, and potassium bicarbonate.

[0162]

[0163] More specifically, the fire extinguishing aid may generate thermal energy together with the chlorate during a fire, and the alkali salt may form alkali radicals due to the generated thermal energy. In this case, the fire extinguishing aid may be, for example, one or more selected from the group consisting of guanidine nitrate, melamine, melamine cyanurate, avicel, guar gum, carboxymethyl, potassium cellulose, dicyandiamide, carboxymethyl cellulose ammonium, nitrocellulose, aluminum, boron, magnesium, magnalium, zirconium, titanium, titanium hydride, tungsten, and silicon.

[0164]

[0165] More specifically, the chlorate may be an oxidizing agent that generates thermal energy through combustion together with the fire extinguishing aid, and the alkali salt may form alkali radicals through the generated thermal energy, and may be, for example, one or more selected from the group consisting of potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, and magnesium chlorate.

[0166]

[0167] More specifically, the fire extinguishing aid and the chlorate may be included in the fire extinguishing agent powder in a weight ratio of 1:9 to 6:4. If the ratio deviates from this, the fire extinguishing performance may be weakened.

[0168]

[0169] More specifically, the alkali salt may be included in an amount of 30 to 1,500 parts by weight per 100 parts by weight of the total of the digestive aid and the chlorate.

[0170]

[0171] More specifically, the thermal decomposition initiation temperature of the fire extinguishing agent powder may be 80°C to 250°C. Since the fire extinguishing agent powder has such a thermal decomposition initiation temperature, the high-heat-resistant resin composition for local fire extinguishing according to the present invention can prevent the occurrence of fire in advance and effectively suppress a fire that has occurred. At this time, the thermal decomposition initiation temperature can be appropriately selected according to the operating environment, and the content of the alkali salt, chlorate, and fire extinguishing aid can also be appropriately adjusted to have the corresponding thermal decomposition initiation temperature.

[0172]

[0173] More specifically, the fire extinguishing agent powder may be included in an amount of 30 to 90 parts by weight per 100 parts by weight of the high heat-resistant resin composition for local fire extinguishing according to the present invention. In this case, if the fire extinguishing agent powder is included in an amount exceeding 90 parts by weight, the proportion of the fire extinguishing agent powder is too high, which may cause problems such as reduced local fire extinguishing effects and excess fire extinguishing reactions due to chain fire extinguishing reactions when a fire occurs. Additionally, if the fire extinguishing agent powder is included in an amount less than 30 parts by weight, there is a problem that the fire extinguishing effect may be reduced due to the proportion of the fire extinguishing agent powder being too low.

[0174] More preferably, the fire extinguishing agent powder may be included in an amount of 40 to 85 parts by weight, and most preferably in an amount of 60 to 80 parts by weight. When the fire extinguishing agent powder is included within this range, the local fire extinguishing performance may be the best.

[0175]

[0176] In particular, in the present invention, the local fire extinguishing performance may be best when the TGA (d50%) value of the siloxane-based resin is included within the range of 350 to 600°C, and at the same time, the fire extinguishing agent powder is included in an amount of 30 to 90 parts by weight per 100 parts by weight of the high heat-resistant resin composition. However, even if a large amount of fire extinguishing agent powder is included, if the heat resistance value of the binder is excessively high, there is a disadvantage that when a fire occurs, the fire extinguishing agent may not react sensitively due to the excessively high heat-resistant binder surrounding the fire extinguishing agent, resulting in reduced extinguishing power or taking a long time to extinguish the fire.

[0177] In addition, even if the TGA value of the binder is within an appropriate range, if an excessive amount of fire extinguishing agent is included, a problem may arise where unnecessary fire extinguishing agent also participates in the reaction due to the exothermic reaction during the fire extinguishing reaction.

[0178] In other words, both the content of the extinguishing agent and the heat resistance of the binder must be controlled within an appropriate range to achieve efficient local extinguishing performance.

[0179]

[0180] Furthermore, when using a fire extinguishing agent powder comprising an alkali salt that generates alkali radicals by thermal energy as described above, a chlorate, and a fire extinguishing aid that generates thermal energy by burning together with the chlorate, this powder possesses excellent fire extinguishing performance because it utilizes a radical reaction in the extinguishing process; however, it is characterized by being equally sensitive to fire. Therefore, when using such a fire extinguishing agent powder, it is particularly necessary to control the content ratio of the powder and the heat resistance of the binder.

[0181] Accordingly, when the TGA (d50%) value of the above siloxane-based resin is 350 to 600°C, preferably 420 to 550°C, and the above fire extinguishing agent powder is included in an amount of 30 to 90 parts by weight, preferably 40 to 85 parts by weight, more preferably 60 to 80 parts by weight, in 100 parts by weight of the high heat-resistant resin composition, the reaction of the fire extinguishing agent unnecessary for fire suppression is blocked, the extinguishing power is improved, and the extinguishing time is shortened, the local fire extinguishing performance can be the best.

[0182]

[0183] More specifically, the fire extinguishing agent powder may have an average diameter of 1 to 200 μm. In this case, if the average diameter of the fire extinguishing agent powder is less than 1 μm, the fire extinguishing agent may react in an area wider than the area where the fire occurred, making it difficult to perform localized fire extinguishing, and if the average diameter of the fire extinguishing agent powder exceeds 200 μm, the fire extinguishing performance may be reduced.

[0184]

[0185] More specifically, the above high-heat-resistant resin composition for local fire extinguishing may further include a dispersant.

[0186] More specifically, the above-mentioned dispersant is not limited to any dispersant that can be typically used in polymer resins, but may be, for example, one or more selected from the group consisting of siloxane-based dispersants, organosilane compound-based dispersants, dispersants having silane heads, polyoxyalkylated alkyl phosphate esters, polydimethylsiloxane-based dispersants, polyoxyethylene siloxane, polyoxypropylene siloxane, methylhydrogenpolysiloxane, alkylsilane-based dispersants, and aminosilane-based dispersants.

[0187] In this case, if the above-mentioned high-heat-resistant resin composition for local fire extinguishing further includes a dispersant, the fire extinguishing agent is uniformly dispersed within the resin composition, thereby enabling the resin composition to exhibit uniform fire extinguishing performance overall, and accordingly, high efficiency of local fire extinguishing performance and fire extinguishing action can be secured.

[0188]

[0189] More specifically, the dispersant may be included in an amount of 0.1 to 3 parts by weight per 100 parts by weight of the high heat-resistant resin composition for local fire extinguishing.

[0190]

[0191] More specifically, the high-heat-resistant resin composition for local fire extinguishing may further include a heat-resistant filler. More specifically, when the heat-resistant filler is further included, the heat resistance is improved, which can enhance the local fire extinguishing ability and enable more efficient fire extinguishing action.

[0192]

[0193] More specifically, the heat-resistant filler may be a hollow filler. A hollow filler is a filler with a hollow interior and is characterized by having strong heat resistance. In this case, the type of hollow filler is not particularly limited, but may be a glass bubble.

[0194] At this time, the average diameter of the hollow filler may be 10 to 100 μm.

[0195]

[0196] At this time, the heat-resistant filler may be included in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the high-heat-resistant resin composition for local fire extinguishing.

[0197]

[0198] More specifically, the above-mentioned high-heat-resistant resin composition for local fire extinguishing may further include additional additives that are typically included as fire extinguishing compositions. In this case, the types of additional additives are not particularly limited, but may include, for example, curing retardants and defoaming agents. Curing retardants delay the curing of siloxane-based resins, allowing the siloxane-based resins to be easily molded into a desired shape, while defoaming agents prevent unwanted defoaming from occurring in the siloxane-based resins.

[0199] More specifically, the curing retardant may be one or more selected from the group consisting of acetylenic alcohols, 1-ethylidene-2-norbornene, maleic acid, maleic anhydride, divinyltetramethyldisiloxane, phenol-based inhibitors, triethyl phosphate (TEP), triphenyl phosphate (TPP), benzoquinone, furan and furan derivatives, thiol compounds, and amine-based inhibitors, and may be included in an amount of 0.01 to 0.5 parts by weight per 100 parts by weight of the high-heat-resistant resin composition for local fire extinguishing.

[0200] More specifically, the defoamer may be one or more selected from the group consisting of polydimethylsiloxane (PDMS), silicone oil, silicone glycol, silicone dioxide, organic modified silicone, polyether defoamers, polypropylene glycol (PPG), stearates, alcohol-based defoamers, mineral oil, and organic defoamers, and may be included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the high heat-resistant resin composition for local fire extinguishing.

[0201]

[0202] More specifically, the binder may be provided in the form of foam. In this case, chemical foaming or physical foaming methods may be used to provide the binder in the form of foam.

[0203] The high-heat-resistant resin composition for local fire extinguishing according to the present invention can suppress a fire by allowing the extinguishing agent to react only with the part where the fire has occurred, so it can exhibit excellent fire extinguishing performance even if the binder is provided in a foam form. In the case of a foam-type binder, it can be particularly effective in preventing fires over a large area.

[0204] More specifically, for chemical foaming, the binder may further include a foaming agent. The foaming agent is not limited to any foaming agent typically used to foam siloxane-based resins, but for example, foaming agents such as azodicarbonamide (ADCA) and hydrazine derivatives may be used. Foaming can be induced by applying heat to the foaming agent or by adding a curing accelerator. In this case, the content of the foaming agent may be 0.5 to 10 parts by weight per 100 parts by weight of the binder.

[0205] More specifically, for physical foaming, a method of injecting gas or the like into the binder may be used. In this case, the type of gas may be N2, CO2, etc., and other foaming conditions are not particularly limited.

[0206]

[0207] Next, a two-component high-heat-resistant resin composition for local fire extinguishing provided by the present invention will be described.

[0208] The present invention provides a two-component high-heat-resistant resin composition for local fire extinguishing that includes a first component comprising vinyl siloxane and a second component comprising hydrogen siloxane to solve the above-mentioned problems, wherein at least one of the first component and the second component further comprises fire extinguishing agent powder.

[0209] More specifically, when the first liquid containing the vinyl siloxane and the second liquid containing the hydrogen siloxane are mixed, the vinyl siloxane and the hydrogen siloxane form a resin through a hydrosilylation reaction. At this time, the resin formed by the hydrosilylation reaction has high heat resistance, and as the fire extinguishing agent is dispersed in this high heat-resistant resin, a high heat-resistant resin composition for local fire extinguishing with high local fire extinguishing ability can be manufactured.

[0210] In addition, when the high-heat-resistant resin for local fire extinguishing according to the present invention is provided as a two-component type, the first and second components only need to be mixed when manufacturing the resin, and there is no need to undergo an additional heating process or UV irradiation process for resin manufacturing, thus preventing the performance of the fire extinguishing agent from being compromised. Furthermore, the high-heat-resistant resin composition for local fire extinguishing according to the present invention is intended to be processed into various forms depending on its application, and since it is composed of two components, it is possible to work at room temperature, making processing into the shape easy and thus allowing for high versatility.

[0211]

[0212] More specifically, the weight ratio of the first liquid and the second liquid may range from 5:1 to 1:1, but preferably may range from 3:1 to 1:1.

[0213]

[0214] First, the first solution will be explained.

[0215] The first solution above contains vinyl siloxane, wherein the vinyl siloxane may be a vinyl siloxane polymer.

[0216] More specifically, the vinyl siloxane may be a siloxane polymer having some alkyl groups as vinyl groups in a siloxane polymer having the following chemical formula 1 as a basic unit.

[0217] <Chemical Formula 1>

[0218]

[0219] (In this case, R1 and R2 are each independently alkyl groups having 1 to 1 carbon atom.)

[0220]

[0221] According to a preferred embodiment of the present invention, the vinyl siloxane of the first liquid may have a Si-Vi content range of 0.05 to 0.5 mmol / g. In this case, if the Si-Vi content is less than 0.05 mmol / g, the hydrosilylation reaction is insufficient, so high heat resistance is not secured and local extinguishing ability may decrease, and if the Si-Vi content exceeds 0.5 mmol / g, the hydrosilylation reaction occurs excessively, so a problem may arise in which the extinguishing ability itself is lowered.

[0222]

[0223] In addition, according to a preferred embodiment of the present invention, the vinyl siloxane of the first liquid may have a viscosity in the range of 50 to 1500 cps.

[0224]

[0225] More specifically, the vinyl siloxane included in the first liquid may be formed by mixing the first vinyl siloxane and the second vinyl siloxane.

[0226] At this time, the first vinyl siloxane has a viscosity of 50 or more and less than 200 cps, and the Si-Vi content may be 0.2 or more and 0.5 mmol / g or less.

[0227] At this time, the second vinyl siloxane has a viscosity of 200 or more and less than 1500 cps, and the Si-Vi content may be 0.05 or more and less than 0.2 mmol / g.

[0228] When the vinyl siloxane included in the first liquid above is a mixture of the first vinyl siloxane and the second vinyl siloxane as described above, when the first liquid is subsequently mixed with the second liquid, the TGA (d50%) value is in the range of 350°C to 600°C, and at the same time, as the fluidity of the formulation is adequately ensured, it can be very excellent in terms of local digestion ability and usability.

[0229] More specifically, the weight ratio of the first vinyl siloxane and the second vinyl siloxane may be in the range of 95:5 to 70:30. If the ratio falls outside this range, when mixed with the second liquid to form a resin, the formulation may be too thin or too thick, which may reduce usability and decrease local digestion performance.

[0230]

[0231] More specifically, the vinyl siloxane included in the first solution may have a network structure. The network structure is not particularly limited as long as it has a conventional network structure, but, for example, it may include the structure of Chemical Formula 6 below.

[0232]

[0233] <Chemical Formula 6>

[0234]

[0235]

[0236] More specifically, some of the alkyl groups bonded to the silicon of the vinyl siloxane included in the first solution may be substituted with any one selected from the group consisting of an aryl group having 3 to 10 carbon atoms and a heteroaryl group having 1 to 10 carbon atoms. Due to this substitution, when some of the silicon of the vinyl siloxane is bonded to an aryl group or a heteroaryl group, the heat resistance of the siloxane resin formed by mixing the first solution and the second solution is improved, and the local fire extinguishing performance may be improved.

[0237] At this time, more specifically, some of the silicon in the vinyl siloxane can be appropriately controlled to have aryl groups and heteroaryl groups so that the TGA (d50%) of the siloxane resin formed when the first and second liquids are mixed has a value of 350 to 600°C.

[0238]

[0239] More specifically, the vinyl siloxane may be included in an amount of 20 to 40 parts by weight per 100 parts by weight of the first liquid.

[0240]

[0241] More specifically, the first liquid may further include a dispersant, wherein the dispersant may be included in an amount of 0.1 to 3 parts by weight per 100 parts by weight of the first liquid. When a dispersant is included, the fire extinguishing agent and the binder are mixed more uniformly, which may reduce manufacturing costs and increase local fire extinguishing performance.

[0242]

[0243] More specifically, the first liquid may further include a fire extinguishing agent, wherein the fire extinguishing agent may be included in an amount of 30 to 90 parts by weight per 100 parts by weight of the first liquid.

[0244]

[0245] More specifically, the first solution may further include a catalyst for a hydrosilylation reaction.

[0246] At this time, the type of catalyst is not particularly limited as long as it can catalyze the hydrosilylation reaction, but it may be one or more selected from the group consisting of Speier catalyst, Karstedt catalyst, platinum catalyst, palladium catalyst, rhodium catalyst, iridium catalyst, nickel catalyst, ruthenium catalyst, cobalt catalyst, iron catalyst, titanium catalyst, zirconium catalyst, lanthanide metal catalyst, copper catalyst, silica-immobilized platinum catalyst, carbon-immobilized platinum catalyst, potassium catalyst, lithium catalyst, aluminum catalyst, indium catalyst, tin catalyst, gold catalyst, polysiloxane-immobilized platinum catalyst, polysiloxane-immobilized palladium catalyst, polysiloxane-immobilized rhodium catalyst, polysiloxane-immobilized ruthenium catalyst, organosilane-modified catalyst, siloxane-ligand-based metal catalyst, and metal siloxane composite catalyst, and preferably may be a platinum catalyst.

[0247] More specifically, the catalyst may be included in a range of 0.01 to 2 parts by weight per 100 parts by weight of the first liquid.

[0248]

[0249] Next, the second amount will be explained.

[0250] The second liquid above contains hydrogen siloxane, wherein the hydrogen siloxane may be a hydrogen siloxane polymer.

[0251] More specifically, the vinyl siloxane may be a siloxane polymer having the following chemical formula 1 as a basic unit, wherein some alkyl groups are substituted with hydrogen.

[0252] <Chemical Formula 1>

[0253]

[0254] (In this case, R1 and R2 are each independently an alkyl group having 1 to 5 carbon atoms.)

[0255]

[0256] According to a preferred embodiment of the present invention, the hydrogen siloxane of the second liquid may have a Si-H content range of 0.5 to 10 mmol / g, and more preferably 4 to 10 mmol / g. In this case, if the Si-H content is less than 0.5 mmol / g, the hydrosilylation reaction is insufficient, so high heat resistance is not secured and the local extinguishing ability may decrease; and if the Si-H content exceeds 10 mmol / g, the hydrosilylation reaction occurs excessively, so the extinguishing ability itself may decrease. In this case, the local extinguishing ability may be best when the Si-H content is in the range of 4 to 10 mmol / g.

[0257]

[0258] More specifically, hydrogen siloxanes can be classified into two-terminal hydrogen siloxanes in which Si-H bonds exist only at both ends, two-terminal and side-chain hydrogen siloxanes in which Si-H bonds exist at both ends and side chains, and side-chain hydrogen siloxanes in which Si-H bonds exist only at the side chains. In this case, the hydrogen siloxane included in the second liquid may be any three types, but preferably, it may be one or more selected from the group consisting of two-terminal and side-chain hydrogen siloxanes and side-chain hydrogen siloxanes, and more preferably, it may be a mixture of two-terminal and side-chain hydrogen siloxanes and side-chain hydrogen siloxanes.

[0259] At this time, the structures of the two end and side chain hydrogen siloxanes are not particularly limited, but for example, the two end and side chain hydrogen siloxanes may be in the form of Chemical Formula 7 below, and the side chain hydrogen siloxanes may be in the form of Chemical Formula 8 below.

[0260]

[0261] <Chemical Formula 7>

[0262]

[0263]

[0264] <Chemical Formula 8>

[0265]

[0266]

[0267] More specifically, the hydrogen siloxane contained in the first solution may have a network structure. The network structure is not particularly limited as long as it has a conventional network structure, but, for example, it may include the structure of Chemical Formula 6 below.

[0268]

[0269] <Chemical Formula 6>

[0270]

[0271]

[0272] In the case where the hydrogen siloxane included in the second liquid above is a mixture of two-terminal and branched-chain hydrogen siloxanes and branched-chain hydrogen siloxanes as described above, when the second liquid is subsequently mixed with the first liquid, the TGA (d50%) value is in the range of 350 to 600°C, and at the same time, as the fluidity of the formulation is adequately ensured, it can be very excellent in terms of local digestion ability and usability.

[0273] More specifically, the weight ratio of the two-terminal / side-chain hydrogen siloxane and the hydrogen siloxane may be 3:7 to 7:3. In this case, if the ratio falls outside this range, when mixed with the first liquid to form a resin, the formulation may be too thin or too thick, which may reduce usability and decrease localized fire extinguishing performance.

[0274]

[0275] More specifically, some of the alkyl groups bonded to the silicon of the hydrogen siloxane included in the second solution may be substituted with any one selected from the group consisting of an aryl group having 3 to 10 carbon atoms and a heteroaryl group having 1 to 10 carbon atoms. When some of the silicon of the hydrogen siloxane is substituted with an aryl group or a heteroaryl group due to substitution, the heat resistance of the siloxane resin formed by mixing the first solution and the second solution is improved, and the local fire extinguishing performance may be improved.

[0276] At this time, more specifically, some of the silicon in the vinyl siloxane can be appropriately controlled to have aryl groups and heteroaryl groups so that the TGA (d50%) of the siloxane resin formed when the first and second liquids are mixed has a value of 350 to 600°C.

[0277]

[0278] More specifically, the hydrogen siloxane may be included in an amount of 20 to 40 parts by weight per 100 parts by weight of the second liquid.

[0279]

[0280] More specifically, the second liquid may further include a dispersant, wherein the dispersant may be included in an amount of 0.1 to 3 parts by weight per 100 parts by weight of the second liquid.

[0281]

[0282] More specifically, the second liquid may further include a fire extinguishing agent, wherein the fire extinguishing agent may be included in an amount of 30 to 90 parts by weight per 100 parts by weight of the second liquid.

[0283]

[0284] More specifically, with respect to 100 parts by weight of the total weight of the first and second liquids, the total weight of the fire extinguishing agent included in the first and second liquids may be in the range of 30 to 90 parts by weight, preferably 40 to 85 parts by weight, and more preferably 60 to 80 parts by weight.

[0285]

[0286] More specifically, the second liquid may contain a small amount of vinyl siloxane to facilitate a smooth hydrosilylation reaction. In this case, the vinyl siloxane may be the first vinyl siloxane described above included in the first liquid. In this case, the first vinyl siloxane may be included in an amount of 5 to 20 parts by weight per 100 parts by weight of the second liquid. If the first vinyl siloxane is included in an amount less than 5 parts by weight, the hydrosilylation reaction may not occur smoothly when mixed with the first liquid, and if it is included in an amount exceeding 20 parts by weight, the local fire extinguishing ability may decrease as the heat resistance becomes too high when mixed with the first liquid.

[0287]

[0288] More specifically, at least one of the first liquid and the second liquid may further include a heat-resistant filler. When at least one of the first liquid and the second liquid includes a heat-resistant filler, the resin formed by mixing the first liquid and the second liquid also includes a heat-resistant filler, and as a result, the heat resistance of the resin formed is improved, so that the local fire extinguishing ability and fire extinguishing efficiency of the high heat-resistant resin composition for local fire extinguishing provided by the present invention can be excellently secured.

[0289] At this time, when the heat-resistant filler is included in the first or second liquid, it may be included in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the first or second liquid.

[0290]

[0291] More specifically, at least one of the first and second liquids may further include a curing retardant. In this case, the curing retardant may be included in an amount of 0.01 to 0.5 parts by weight per 100 parts by weight of the first or second liquid.

[0292] More specifically, at least one of the first and second solutions may further include an antifoaming agent. In this case, the curing retardant may be included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the first or second solution.

[0293]

[0294] More specifically, when the first liquid and the second liquid are mixed to form a resin, the resin may be provided in the form of a foam, and for this purpose, at least one of the first liquid and the second liquid may further include a foaming agent. In this case, the content of the foaming agent may be 0.5 to 10 parts by weight per 100 parts by weight of the first liquid or the second liquid.

[0295]

[0296] Next, the battery module provided by the present invention will be described.

[0297] The statement that a component is "in front," "rear," "upper," or "lower" of another component includes, unless there are special circumstances, not only being positioned "in front," "rear," "upper," or "lower" in direct contact with the other component, but also cases where another component is positioned in between. Furthermore, the statement that a component is "connected" to another component includes, unless there are special circumstances, not only being directly connected to each other, but also being indirectly connected to each other.

[0298] Hereinafter, a battery module (100) having a extinguishing layer formed according to the present invention is described with reference to the drawings.

[0299] Hereinafter, a battery module (100) having a extinguishing layer formed thereon according to a preferred embodiment of the present invention is described with reference to the drawings.

[0300] Before describing the battery module (100) having a extinguishing layer formed according to the present embodiment, a general pouch-type battery cell (10) will be described.

[0301] FIG. 11 (a) is a drawing showing the pouch (12) of a pouch-shaped battery cell (10) in an open state before being folded, and FIG. 11 (b) is a drawing showing the battery cell (10) with the pouch (12) folded.

[0302] A pouch-type battery cell (10) may include an electrode (11), a pouch (12), and a lead tab (16), as shown in FIG. 11 (a) and (b).

[0303] The above electrode (11) can have a positive electrode and a negative electrode stacked in a rectangular shape.

[0304] Additionally, the pouch (12) can serve as an outer shell that encloses the electrode (11). That is, the pouch (12) forms a receiving space in which the electrode (11) is received, and can serve as an outer shell that encloses the electrode (11) and protects it from the outside.

[0305] The above pouch (12) may be made of a film or the like, which has a synthetic resin such as polyethylene terephthalate (PET) coated on the surface of a metal material such as aluminum.

[0306] The above pouch (12) has a pocket (15) formed therein for accommodating the electrode (11) and the electrolyte, and surrounds the electrode (11) to protect the electrode (11) and the electrolyte from the outside and prevent the electrolyte inside from leaking out.

[0307] The above pouch (12) includes a first outer layer (13) forming a first surface of the pocket (15) and a second outer layer (14) forming a second surface of the pocket (15), and the first outer layer (13) and the second outer layer (14) can form a sealing portion (21) joined together at the outer edge of the pocket (15).

[0308] The pocket (15) may be formed only in the first outer layer (13) or may be formed in both the first outer layer (13) and the second outer layer (14).

[0309] Additionally, the lead tab (16) may be formed to extend from the electrode (11) to the outside of the pouch (12) in order to electrically connect the electrode (11) to the outside.

[0310] The above lead tab (16) may be coated with a synthetic resin film such as polypropylene (PP) on the surface of an electrically conductive metal.

[0311] Additionally, the pocket (15) may be formed by being recessed into the first outer layer (13) to form a space in which the electrode (11) and the electrolyte are received.

[0312] Meanwhile, the first outer layer (13) and the second outer layer (14) are formed integrally as shown in FIG. 1 (a), and as shown in FIG. 11 (b), after the electrode (11) is placed, they can be folded and overlapped to be joined to form a sealing portion (21).

[0313] Figure 12 (a) is a plan view of a pouch-type battery cell, (b) is a cross-sectional view of AA, and (c) is a cross-sectional view of BB.

[0314] As shown in FIG. 2, the sealing portion (21) may be composed of a pair of short portions (24) on the side where the lead tab (16) is located and a pair of long portions (21) that are orthogonal to the short portions (24) and longer than the short portions (24).

[0315] The above-mentioned long side portion (21) may also include a first long side portion (22) at the end where the first outer skin layer (13) and the second outer skin layer (14) are folded, and a second long side portion (23) on the side facing the first long side portion (22).

[0316] Meanwhile, when gas or the like is generated during the use of the battery cell (10) and the pressure inside the pocket (15) increases, the pressure of the gas acts on the sealing part (21). At this time, since the length of the long side (21) of the sealing part (21) is longer than the short side (24), the long side (21) is a more vulnerable part than the short side (24).

[0317] The above long side (21) is also more vulnerable in the second long side (23), where the first outer skin layer (13) and the second outer skin layer (14) are joined to form a discontinuous surface, than in the first long side (22), where the first outer skin layer (13) and the second outer skin layer (14) are folded to form a continuous surface.

[0318] In particular, the central region of the second side (23) may be the most vulnerable. This is because the gas pressure acts as a uniformly distributed load on the sealing part (21), and the shear force acts to the maximum at the center point of the longest side.

[0319] Therefore, the central area of ​​the second side section (23) is the point most vulnerable to gas pressure, and thus, gas leakage may first start in the central area of ​​the second side section (23).

[0320] Hereinafter, in the first embodiment of the present invention, the central point of the second length portion (23) is referred to as the leakage risk area (30) where gas leakage may first begin.

[0321] If gas and electrolyte leak in the above leakage risk area (30), the leaked gas and electrolyte may react with oxygen in the atmosphere and start a fire. Therefore, the above leakage risk area (30) may be a fire risk area where a fire first occurs.

[0322] FIG. 13 is a drawing illustrating a battery module (100) having a extinguishing layer formed thereon according to a preferred embodiment of the present invention.

[0323] A battery module (100) may refer to a unit in which a plurality of battery cells (10) are housed in an enclosure.

[0324] A battery module (100) having a extinguishing layer formed according to the present embodiment may include a battery cell (10), a casing (110), and a extinguishing layer (120), as shown in FIG. 11.

[0325] In a preferred embodiment of the present invention, the battery cell (10) may be the aforementioned pouch-type battery cell (10).

[0326] The above casing (110) is formed in the shape of a roughly rectangular parallelepiped and can accommodate multiple pouch-shaped battery cells (10) inside.

[0327] The above fire extinguishing layer (120) may be formed by applying a high heat-resistant resin composition for local fire extinguishing according to the present invention to the inner surface of the casing (110) facing the battery cell (10), specifically the surface facing the leakage risk area (30) of the battery cell (10).

[0328] The above-mentioned extinguishing layer (120) may be a layer coated with a high heat-resistant resin composition for local extinguishing according to the present invention.

[0329] The above-mentioned extinguishing layer (120) is a layer containing the above-mentioned high-heat-resistant resin composition for local extinguishing, and when a fire occurs in the secondary battery cell, the extinguishing material can perform a extinguishing action.

[0330] The above-mentioned extinguishing layer (120) can be formed in the form of a paste or paint containing the above-mentioned high-heat-resistant resin composition for local extinguishing, or by coating, printing, or spraying.

[0331] Accordingly, by forming a fire extinguishing layer (120) on the inner surface of the casing (110) facing the leakage risk area (30) of the battery cell (10), the fire that occurs can be suppressed in the early stages or the spread of the fire can be delayed to secure time for response.

[0332] Meanwhile, as illustrated in FIG. 13, when the pouch-shaped battery cell (10) is placed within the casing (110), the battery cell (10) may be positioned such that the second side portion (23) where the leakage risk area (30) is formed faces the upper side of the casing (110).

[0333] In this case, the digestion layer (120) may be formed on the inner surface of the surface forming the upper surface (112) of the casing (110).

[0334] Alternatively, when the pouch-shaped battery cell (10) is placed in the casing (110), such as in the battery module (100) formed with a fire extinguishing layer according to a preferred embodiment of the present invention shown in FIG. 14, some of the battery cells (10) may be arranged such that the second side portion (23) where the leakage risk area (30) is formed faces the upper side of the casing (110), and the rest may be arranged such that the second side portion (23) where the leakage risk area (30) is formed faces the upper side of the casing (110).

[0335] In this case, the digestion layer (120) may be formed on the inner surface of the upper surface (112) and lower surface (114) of the casing (110).

[0336] Alternatively, although not illustrated in the drawing, the second side portion (23) in which the leakage risk area (30) of the battery cell (10) is formed may be arranged to face the lower side of the casing (110), and the fire extinguishing layer (120) may be formed on the inner side of the surface forming the lower surface (114) of the casing (110).

[0337] FIG. 15 is a drawing illustrating the pattern of a fire extinguishing layer (120) formed on the inner surface of a casing (110) of a battery module (100) having a fire extinguishing layer formed according to the first and second embodiments of the present invention.

[0338] The above-mentioned fire extinguishing layer (120) can be formed on the entire surface facing the leakage risk area (30) of the battery cell (10) among the inner surfaces of the casing (110) facing the battery cell (10).

[0339] Alternatively, the fire extinguishing layer (120) may be formed in a strip-like pattern on the inner surface facing the battery cell (10) of the casing (110), specifically on the surface facing the leakage risk area (30) of the battery cell (10), thereby reducing waste of fire extinguishing material.

[0340] That is, as illustrated in FIG. 15 (a), the fire extinguishing layer (120) may include a plurality of first straps (122) applied in a line form along the second long side (23) at a position facing the second long side (23) where the leakage risk area (30) of each battery cell (10) is formed on the inner surface of the casing (110) facing the leakage risk area (30) of the battery cell (10).

[0341] That is, the fire extinguishing substance is applied only to the area facing the second side section (23), which is the point where gas or electrolyte leakage or fire occurs.

[0342] Therefore, the above-mentioned extinguishing material can be used more efficiently.

[0343] At this time, as shown in Fig. 15 (b), the central part facing the leakage risk area (30), which is the point where gas or electrolyte leakage or fire occurs in the first strap (122a), is formed with a thicker width than the rest, so that the fire suppression and propagation delay effects can be further improved.

[0344] Alternatively, as shown in Fig. 15 (c), a second strap (124) may be further formed in the form of a line that is orthogonal to the first strap (122) and crosses the middle portion of the plurality of first straps (122).

[0345] The second strap (124) may be formed to cross the middle portion of the first strap (122) which is located facing the leakage risk area (30).

[0346] Meanwhile, the lead tab (16) is coated with a synthetic resin such as a PP film on the surface of an electrically conductive metal piece, and the film layers of the first outer layer (13) and the second outer layer (14) forming the pouch (12) can be heat-fused with the film layers of the lead tab (16) to form a short side portion (24) of the sealing portion (21).

[0347] However, compared to the long side (21) where the same material is heat-fused, the bonding strength of the short side (24) where a different material is fused may be lower.

[0348] This suggests that when the pressure inside the pocket (15) of the pouch (12) rises, there is a high probability that leakage will occur first at the short side (24) compared to other parts, and therefore there is a possibility that a fire may occur at the short side (24). In this case, the short side (24) may become a leakage risk area where leakage of gas or electrolyte may begin.

[0349] Accordingly, the first and second embodiments of the present invention may include a heat transfer prevention unit (130) containing a heat transfer prevention material and a fire extinguishing material, which is disposed in the space between the lead tabs (16) of mutually adjacent battery cells (10) among the plurality of battery cells (10) as shown in FIG. 6 (a).

[0350] That is, since the pocket (15) portion of the pouch (12) type battery cell (10) protrudes bulgingly, a space is formed between the lead tabs (16) of mutually adjacent battery cells (10), and a heat transfer prevention unit (130) is placed in that space.

[0351] At this time, the heat transfer prevention unit (130) is not specifically limited in shape as long as it is a unit capable of extinguishing a fire in the event of a fire, and can be appropriately selected according to the shape of the battery module, etc., and may be, for example, a capsule type or a sheet type. At this time, a capsule type heat transfer prevention unit is shown in FIG. 6, but it is not limited thereto.

[0352] At this time, the heat transfer prevention unit (130) may be a capsule or sheet that blocks heat from being transferred to an adjacent battery cell (10) and simultaneously extinguishes a fire when a fire occurs.

[0353] The above heat transfer prevention unit (130) may include an outer shell (132), a binder (134), and a fire extinguishing agent powder (136), as shown in FIG. 16 (b).

[0354] The outer shell (132) may be made of a film made of a synthetic resin material such as polypropylene (PP). The outer shell (132) may be formed in the shape of a hollow pipe with both ends closed to form a space inside which the binder (134) and fire extinguishing agent powder (136) are contained.

[0355] The above binder and fire extinguishing agent powder are as described above, so their description is omitted.

[0356] The binder (134) and the fire extinguishing agent powder (136) are mixed into the outer shell (132) to provide heat blocking and fire extinguishing capabilities.

[0357] At this time, the heat transfer prevention unit (130) may be extended to have a longitudinal direction in the direction of the short side (24) of the battery cell (10).

[0358] That is, when a fire occurs in the short side (24) of the battery cell (10), the outer shell (132) melts and the fire is extinguished by the fire extinguishing agent powder (136). In the case of the fire extinguishing agent powder (136) in the heat transfer prevention unit (130) that is not adjacent to the battery cell (10) where the fire occurred, it does not reach a temperature sufficient for the extinguishing reaction due to the binder (134) and therefore does not participate in the reaction. Accordingly, only the fire extinguishing agent powder (136) near the cell where the fire occurred reacts, allowing the fire to be suppressed locally and efficiently, and preventing subsequent continuous fires.

[0359] Therefore, even if leakage and fire occur in the long side (21) and short side (24) of the pouch (12) type battery cell (10) housed in the battery module (100), they can be easily extinguished.

[0360]

[0361] The present invention will be explained more specifically through the following examples, but the following examples are not intended to limit the scope of the invention and should be interpreted as being for the purpose of aiding understanding of the invention.

[0362]

[0363] <Example 1>

[0364] A first liquid was prepared by mixing a first vinyl siloxane (VEP-100, Si-Vi content (mmol / g) : 0.37, viscosity 100 cps) and a second vinyl siloxane (VEP-1000, Si-Vi content (mmol / g) : 0.11, viscosity 1000 cps), a Pt catalyst (CAT5000), a dispersant (BYK LP-X 25383), and fire extinguishing agent powder. Subsequently, a second liquid was prepared by mixing a two-part, side-chain hydrogen siloxane (FD5022, Si-H content (mmol / g) : 1), a side-chain hydrogen siloxane (FD5038, Si-H content (mmol / g) : 1.2), a vinyl siloxane (VEP-100, Si-Vi content (mmol / g) : 0.37, viscosity 100 cps), a dispersant (BYK LP-X 25383), and a fire extinguishing agent powder. Subsequently, the first liquid and the second liquid were mixed in a weight ratio of 2 to 1 to prepare a high-heat-resistant resin composition for local fire extinguishing according to the present invention, and the composition was molded into the form provided in the following examples to conduct experiments.

[0365] At this time, the fire extinguishing agent powder was made to contain an alkali salt (tripotassium citrate), a chlorate (potassium chlorate), and a fire extinguishing aid (sodium carboxymethyl cellulose) in a weight ratio of 50:36:14, and the average diameter was made to be 8.9 μm.

[0366] Table 1 below shows the weight percentage of the components included in the first and second liquids for each example.

[0367]

[0368] <Example 2>

[0369] The second solution was prepared in the same manner as Example 1, except for the use of a double-sided, branched-chain hydrogen siloxane (FD5021, Si-H content (mmol / g) : 4.2) and the difference shown in Table 1 below.

[0370]

[0371] <Example 3>

[0372] In the second solution, bilateral branched-chain hydrogen siloxane (FD5021, Si-H content (mmol / g) : 4.2) and branched-chain hydrogen siloxane (MH-75, Si-H content (mmol / g) : 7.5) were used; in the first solution, glass bubbles (iM16k) were additionally added; and the apparent density of the fire extinguishing agent powder is 1.4 g / cm³ 3 It was manufactured in the same manner as Example 1, except for the difference in the following Table 1 and the fact that it was made to be so.

[0373]

[0374] <Comparative Example 1>

[0375] In the above Example 1, only the fire extinguishing agent was prepared.

[0376]

[0377] Liquid 1, 1st Vinylsiloxane, 2nd Vinylsiloxane, Pt Catalyst Dispersant, Glass Bubble Fire Extinguishing Agent Powder Example 1: 24.92.80.81.1070.4 Example 2: 19.48.30.81.1070.4 Example 3: 17.87.60.71.32.670 Liquid 2, Two-ended / Side-chain Hydrogensiloxane, Side-chain Hydrogensiloxane, Vinylsiloxane Dispersant, Fire Extinguishing Agent Powder Example 1: 77141.870.2 Example 2: 77141.870.2 Example 3: 39.39.39.31.970.2

[0378]

[0379] <Experimental Example 1 - Measurement of TGA (d50%) Value>

[0380] To evaluate the heat resistance of the binder used in each example, a binder was prepared by mixing the first and second liquids of each example after excluding the dispersant, glass bubbles, and fire extinguishing agent powder. Subsequently, the TGA (d50%) value was evaluated for the binder corresponding to each example using a Q50 (TA Instruments) instrument, and the evaluation conditions were set at a heating rate of 10℃ / min up to 500℃. The results of the TGA value evaluation are shown in Figure 1, and the TGA (d50%) value was measured and is shown in Table 2.

[0381]

[0382] TGA(d50%) Example 1403.02 Example 2433.96 Example 3481.26

[0383]

[0384] As can be seen in Table 2, it can be confirmed that all of Examples 1 to 3 have TGA (d50%) values ​​within the range of 350 to 600°C.

[0385]

[0386] <Experimental Example 2 - Torch Evaluation 1>

[0387] After mixing the first and second solutions of each example, apply to a tray, react and dry at 70°C for 6 hours to obtain 25X12X0.15(cm) 3 A sheet of ) was manufactured. In the case of Comparative Example 1, since the fire extinguishing agent is in powder form, it was prepared in powder form.

[0388] Subsequently, for each example and comparative example, the extinguishing ability was evaluated by firing a flame for 1 second from a distance of 2 cm in each experimental example and example using a gas torch (HONEST gas torch). An evaluation photograph for Example 1 is shown in FIG. 2, and an evaluation photograph for Comparative Example 1 is shown in FIG. 3.

[0389] For Examples 1 to 3, 10 flames were fired and the average diameter of the flame traces was measured and shown in Table 3.

[0390]

[0391] Average diameter of torch marks (mm) Example 1 15.4 ± 1.2 Example 2 13.8 ± 0.9 Example 3 13.3 ± 1.4

[0392]

[0393] First, as can be seen from FIGS. 2 and FIGS. 3, it was confirmed that in the case of Examples 1 to 3, even though a flame was applied, extinguishing action occurred only in the area where the flame was applied, showing localized extinguishing performance. However, in the case of Comparative Example 1, even though the same extinguishing agent was used, it was confirmed that all of the extinguishing agent reacted with a single contact with flame due to the absence of a binder, and that no extinguishing action was shown in subsequent secondary contact with flame. In conclusion, it can be confirmed that Examples 1 to 3 all have localized extinguishing performance, but Comparative Example 1 does not.

[0394] In addition, referring to Table 3, it can be observed that the torch marks become smaller as one moves from Example 1 to Example 3. This can be understood as the range of extinguishing agents that participated in the extinguishing reaction when a flame was applied, and it is consistent with the trend of increasing TGA (d50%). In other words, it can be confirmed that local extinguishing performance improves as the TGA (d50%) value increases. However, if the TGA (d50%) is 600°C or higher, there is a concern that the extinguishing performance may decrease in the event of a fire due to excessively high heat resistance.

[0395]

[0396] <Experimental Example 3 - Torch Evaluation 2>

[0397] After preparing a cylindrical capsule made of polypropylene material with a diameter of 1.2 cm and a height of 10 cm, the composition and digestive agent according to each example and comparative example were added and sealed.

[0398] Subsequently, the extinguishing ability of each example and comparative example was evaluated by using a gas torch (HONEST gas torch) to fire a flame for 1 second from a distance of 2 cm at each example and comparative example, on the capsule into which the composition and extinguishing agent were introduced. An evaluation photograph for Example 1 is shown in Fig. 4, and an evaluation photograph for Comparative Example 1 is shown in Fig. 5.

[0399] As can be seen from FIGS. 4 and 5, in Examples 1 to 3, even if multiple flames are applied, the extinguishing action occurs only in the relevant area, and a continuous extinguishing reaction is possible when flames are subsequently applied to other areas, whereas in Comparative Example 1, all extinguishing agents participate in the reaction with a single extinguishing, and it can be seen that extinguishing is impossible at all after a second flame is applied.

[0400]

[0401] <Experimental Example 4 - Battery Penetration Evaluation>

[0402] Sheet-shaped (30X15X0.1cm) on the wall of the evaluation chamber as shown in Fig. 6 3 After placing the high-heat-resistant resin compositions for local fire suppression of Examples 1 to 3, prepared by ), two battery cells (60Ah pouch cells, Goodbye Car) were laid flat in front of them to prepare for a penetration evaluation. Subsequently, an awl with a diameter of 1 mm was made to penetrate the battery at a speed of 0.1 mm / s from the center of the battery. After penetrating one battery located at the top, the awl stopped moving. Photographs of the experimental results and process of Example 1 are shown in FIG. 7, and the results of the evaluation for Examples 1 to 3 are shown in Table 4.

[0403]

[0404] Upper cell thermal runaway status Lower cell thermal runaway status Fire extinguishing sheet ignition area (cm 2 Example 1 OX 30x8.1 Example 2 OX 30x6.2 Example 3 OX 30x5.3

[0405]

[0406] As can be seen from FIGS. 6, FIGS. 7, and Table 4, in the cases of Examples 1 to 3, it can be confirmed that thermal runaway occurred due to penetration in the upper cell, but thermal runaway did not occur in the lower cell. In the case of a battery, when thermal runaway occurs, the two electrodes are directly connected, causing an explosive chemical reaction and continuously releasing a large amount of heat. The fact that thermal runaway did not occur in the lower cell means that the fire caused by thermal runaway in the upper cell was completely extinguished before it could cause thermal runaway in the lower cell. In other words, the high-heat-resistant resin composition for local fire extinguishing according to the present invention can be said to be excellent in terms of its fire extinguishing power.

[0407] In addition, looking at the photograph of the fire extinguishing sheet after the extinguishing reaction, it can be seen that the extinguishing agent did not react at all except for the area where the battery ignited and caused a fire. This indicates that the local extinguishing performance of the resin composition according to the present invention is excellent. Furthermore, regarding the ignition area, it can be confirmed that the area decreases as it progresses from Experimental Example 2 to Example 3. Through this, it can be confirmed that the local extinguishing performance increases as the TGA (d50%) value increases. However, if the TGA (d50%) is 600°C or higher, there is a concern that the extinguishing performance may decrease in the event of a fire due to excessively high heat resistance.

[0408]

[0409] <Experimental Example 5 - Battery Heating Evaluation>

[0410] The fire extinguishing composition and extinguishing agent according to each example and comparative example were placed into cylindrical capsules made of polypropylene material with a diameter of 1.2 cm and a height of 10 cm. Subsequently, as shown in Fig. 8, four batteries were stacked, and six of the corresponding capsules were placed at the edges between each battery, with a heating pad placed on top. In addition, since this experiment aimed to measure the fire extinguishing performance when the batteries sequentially underwent thermal runaway, a thermal barrier (mica sheet) was placed between the battery cells to prevent the cells from running away simultaneously. After closing the evaluation chamber, the heating pad was activated to induce thermal runaway starting from the uppermost cell, and then it was observed whether the fire caused by the thermal runaway of each cell could be suppressed. A photograph evaluating Example 1 is shown in Fig. 9, and a photograph evaluating Comparative Example 1 is shown in Fig. 10. Table 5 indicates whether each example and comparative example suppressed the fire that occurred when thermal runaway occurred in each cell. The battery cells were named 1, 2, 3, and 3 from the top downwards.

[0411]

[0412] Fire suppression status Cell 1 Cell 2 Cell 3 Cell 4 Example 1OOOO Example 2OOOO Example 3OOOO Comparative Example 1OOOX

[0413]

[0414] As can be seen from FIGS. 8 to 10 and Table 5, in the case of Comparative Example 1, in which only a fire extinguishing agent was introduced, when a fire occurred in Cell 3, all the fire extinguishing agents contained in the capsules near Cell 4 reacted as a result, and when thermal runaway occurred in Cell 4, it was confirmed that fire suppression was impossible. In contrast, in the case of Examples 1 to 3, after a fire occurred, the composition inside the capsules reacted sequentially, and it was possible to suppress the fire caused by all thermal runaway up to Cell 4.

[0415] In the case of batteries used in actual automobiles, etc., most of the cells within a single module have similar charge-discharge cycles, so thermal runaway may occur at similar times, and there is also a sufficient possibility that thermal runaway may occur continuously if a problem occurs within the module. Accordingly, it can be confirmed through Experimental Example 5 that the fire extinguishing composition according to the present invention is capable of sufficiently responding to such continuous thermal runaway of the battery.

[0416]

[0417] <Experimental Example 6 - Evaluation of Local Fire Extinguishing Ability and Extinguishing Power According to Fire Extinguishing Agent Powder Content>

[0418] In each example, the local fire extinguishing ability was evaluated while varying the weight percentage of the fire extinguishing agent powder. In each example, experiments were conducted by varying the weight percentage of the fire extinguishing agent powder as shown in Table 7 below. In this case, when less fire extinguishing agent powder was added than in Table 1, an equal weight of binder was added, and when more fire extinguishing agent powder was added than in Table 1, an equal weight of binder was added. The weight percentage of the fire extinguishing agent powder was varied for both the first and second liquids. Subsequently, the composition according to each example was applied to a tray, reacted and dried at 70°C for 6 hours, and 10 x 10 x 0.1 cm² 3 A sheet was manufactured. A wire mesh was placed on a support, and the fire extinguishing sheet was placed in the center. A torch was positioned 5 cm below it, lit, and then covered with a container. After the torch flame was extinguished, the area of ​​the sheet where the fire extinguishing agent reacted and the thickness of the activated fire extinguishing sheet were measured and recorded in Table 6. For each case, measurements were taken three times, and the average value was recorded.

[0419]

[0420] Fire extinguishing agent powder content (weight%), extinguishing part, average reaction area (cm²) 2) Thickness of the extinguished area remaining after evaluation (μm) Example 1 20 extinguishing failure 5x5.5 puncture 40 extinguished 4x4.5 200 70 extinguished 4x4 400 Example 2 20 extinguishing failure 5x5.5 puncture 40 extinguished 4x4.5 250 70 extinguished 4x3.5 450 Example 3 20 extinguishing failure 5x5 puncture 40 extinguished 4x4 300 70 extinguished 3.5x3.5 550

[0421]

[0422] Looking at Table 6, the average reaction area refers to the range of the extinguishing agent that reacted to extinguish the same fire, so a smaller average reaction area indicates superior local extinguishing ability. Additionally, the remaining thickness of the extinguished area after evaluation indicates that the fire was suppressed more quickly the thicker it is, so a thicker thickness indicates superior extinguishing power.

[0423] In Examples 1 to 3, when the content of the extinguishing agent powder was less than 30 parts by weight relative to the resin composition, extinguishing failed; consequently, it was observed that the reaction area was very large and the extinguishing atmosphere was penetrated after the evaluation was completed. In contrast, when the content of the extinguishing agent powder was in the range of 30 to 90 parts by weight, extinguishing was successful; the reaction area was small, and even after the evaluation was completed, the extinguishing atmosphere was not penetrated and remained with a specific thickness. In particular, when the content of the extinguishing agent powder was 60 to 80 parts by weight, the reaction area was the smallest and the thickness of the extinguished area after evaluation was the thickest, confirming that the local extinguishing ability and extinguishing power were the best.

[0424] Furthermore, it can be seen that the extinguishing power and local extinguishing ability improve as one moves from Example 1 to Example 3, which is consistent with the trend of increasing TGA (d50%). In other words, it can be confirmed that the local extinguishing ability and extinguishing power increase as the TGA (d50%) value increases. However, if the TGA (d50%) is 600°C or higher, there is a concern that the extinguishing performance may decrease in the event of a fire due to excessively high heat resistance.

[0425]

[0426] [Explanation of the symbol]

[0427] 10: Battery cell 11: Electrode

[0428] 12: Pouch 13: First outer layer

[0429] 14: Second outer layer 15: Pocket

[0430] 16: Lead tab 20: Sealing part

[0431] 21: Long side section 22: First long side section

[0432] 23: Chapter 2 Side Section 24: Short Side Section

[0433] 30: Leakage Risk Area

[0434] 100: Battery module 110: Casing

[0435] 112: Top surface 114: Bottom surface

[0436] 120: Digestion layer 122: First strap

[0437] 124: Second strap 130: Heat transfer prevention unit

[0438] 132: Outer shell 134: Binder

[0439] 136: Digestive agent powder

Claims

1. A binder comprising a siloxane-based resin having repeating units of the following chemical formula 1; and A high-heat-resistant resin composition for local fire extinguishing comprising fire extinguishing agent powder dispersed within the binder. <Chemical Formula 1> (In this case, R1 and R2 are each independently an alkyl group having 1 to 10 carbon atoms.) 2. In Paragraph 1, A high-heat-resistant resin composition for local fire extinguishing, characterized in that the above siloxane-based resin has a TGA (d50%) value of 350 to 600°C.

3. In Paragraph 1, A high-heat-resistant resin composition for local fire extinguishing, characterized in that the above-mentioned siloxane-based resin is formed through a hydrosilylation reaction.

4. In Paragraph 1, A high-heat-resistant resin composition for local fire extinguishing, characterized in that the above-mentioned fire extinguishing agent powder is included in an amount of 30 to 90 parts by weight per 100 parts by weight of the above-mentioned high-heat-resistant resin composition for local fire extinguishing.

5. In Paragraph 1, A high-heat-resistant resin composition for local fire extinguishing, characterized in that the above-mentioned fire extinguishing agent powder is included in an amount of 60 to 80 parts by weight per 100 parts by weight of the above-mentioned high-heat-resistant resin composition for local fire extinguishing.

6. In Paragraph 1, The above high-heat-resistant resin composition for local fire extinguishing is characterized by further including a dispersant.

7. In Paragraph 1, The above high-heat-resistant resin composition for local fire extinguishing is characterized by further including a heat-resistant filler.

8. In Paragraph 7, A high-heat-resistant resin composition for local fire suppression, characterized in that the heat-resistant filler is a hollow filler.

9. In Paragraph 1, The above fire extinguishing agent powder is Alkali salts that generate alkali radicals through thermal energy, A high-heat-resistant resin composition for local fire extinguishing characterized by comprising a chlorate and a fire extinguishing aid that burns together with the chlorate to generate thermal energy.

10. In Paragraph 1, A high-heat-resistant resin composition for local fire extinguishing, characterized in that the average diameter of the fire extinguishing agent powder is 1 to 200 μm.

11. A first solution comprising vinyl siloxane; and A second solution comprising hydrogen siloxane; comprising, A two-component high-heat-resistant resin composition for local fire extinguishing in which at least one of the first and second components further comprises fire extinguishing agent powder.

12. In Paragraph 11, The above first liquid comprises a first vinyl siloxane and a second vinyl siloxane, and The first vinyl siloxane has a viscosity of 50 or more and less than 200 cps, and a Si-Vi content of 0.2 or more and 0.5 mmol / g or less, and The above-mentioned second vinyl siloxane is characterized by having a viscosity of 200 or more and less than 1500 cps, and a Si-Vi content of 0.05 or more and less than 0.2 mmol / g, Two-component high-heat-resistant resin composition for local fire extinguishing.

13. In Paragraph 12, A two-component high-heat-resistant resin composition for local fire extinguishing, characterized in that the weight ratio of the first vinyl siloxane and the second vinyl siloxane is 95:5 to 70:

30.

14. In Paragraph 11, A two-component high-heat-resistant resin composition for local fire extinguishing, characterized in that the second component comprises a two-terminal / side-chain type hydrogen siloxane and a side-chain type hydrogen siloxane.

15. In Paragraph 11, A two-component high-heat-resistant resin composition for local fire extinguishing, characterized in that at least one of the first liquid and the second liquid further comprises a heat-resistant filler.

16. In Paragraph 11, The above fire extinguishing agent powder is, Alkali salts that generate alkali radicals through thermal energy, A two-component high-heat-resistant resin composition for local fire extinguishing, characterized by comprising a chlorate and a fire extinguishing aid that burns together with the chlorate to generate thermal energy.

17. One or more battery cells; A casing accommodating the above plurality of battery cells; Among the inner surfaces of the casing facing the battery cell, leakage of the battery cell A battery module having a fire extinguishing layer formed thereon, comprising: a fire extinguishing layer having a high heat-resistant resin composition for local fire extinguishing according to any one of claims 1 to 16 applied to the surface facing the danger area.

18. In Paragraph 17, The above battery cell is, electrode; A pocket is formed to accommodate the electrode and electrolyte, and the electrode is surrounded and protected from the outside, and the first outer layer forming the first surface of the pocket and the second outer layer forming the second surface of the pocket are included, wherein the first outer layer and the second outer layer are formed integrally. A pouch that folds and overlaps each other to form a sealing portion joined together at the outer edge of the pocket; and A lead tab extending from the electrode to the outside of the pouch; comprising The sealing portion comprises a pair of short sides on the side where the lead tab is located and a pair of long sides that are orthogonal to the short sides and longer than the short sides. The above leakage risk area is the central area of ​​the side facing the folding side among the above long sides, and A battery module having a fire extinguishing layer formed thereon, further comprising a heat transfer prevention unit disposed in the space between the lead tabs of mutually adjacent battery cells among the plurality of battery cells, and comprising a high heat-resistant resin composition for local fire extinguishing according to any one of claims 1 to 16.

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