KR102391491B1 - Curable Composition - Google Patents

Abstract

This application relates to curable compositions and uses thereof. The present application may provide a curable composition excellent in one or more or all properties selected from adhesion, insulation, curability and thermal conductivity, or use of such a curable composition or cured product.

Description

Curable Composition

This application relates to curable compositions and uses thereof.

As the use of batteries such as secondary batteries is extended to medium and large devices such as automobiles or power storage devices, high output is required, and accordingly, high integration of battery cells (unit cells) is required.

Since highly integrated battery cells emit a lot of heat during operation, excellent cooling performance must be secured.

Patent Document 1 proposes a method of imparting stable cooling performance to a battery module including highly integrated battery cells by applying an adhesive containing an excess of thermally conductive filler.

In order for the battery module such as Patent Document 1 to stably drive and exhibit desired performance, the adhesive should exhibit stable adhesion to the battery cell along with high thermal conductivity. If the adhesive strength of the adhesive is low, it cannot effectively respond to vibrations or shocks generated during the use of the battery module. In particular, since the outermost layer of the battery cell is typically a polyester material such as a PET (poly(ethylene terephthalate)) film, the adhesive should exhibit excellent adhesion to the polyester material.

In addition, since the application of heat during curing of the adhesive is limited in consideration of the thermal stability of the battery cell, the adhesive needs to be curable at room temperature as much as possible.

In addition, excellent electrical insulation is also required for the adhesive as described above.

Among adhesive materials, a so-called polyurethane adhesive is suitable for a battery module having the same structure as in Patent Document 1 because it satisfies the above characteristics relatively well.

However, the polyurethane adhesive includes an isocyanate compound as a curing agent, and since this curing agent has reactivity with moisture, storage stability is weak, and it may react with moisture present in a filler included in a large amount in the adhesive to cause problems. .

As an adhesive material capable of solving the above problems, an epoxy material may be considered. However, since the epoxy material has poor adhesion to the polyester material having a relatively low surface energy, it is difficult to secure stable adhesion to the battery cell. Moreover, it is not an easy task to provide stable adhesion to battery cells and electrical insulation to an epoxy material containing a high content of filler in order to secure thermal conductivity.

Korean Patent Publication No. 2016-0105354

An object of the present application is to provide a curable composition excellent in one or more or all properties selected from adhesion, insulation, curability and thermal conductivity, or use of such a curable composition or cured product.

Among the physical properties mentioned in this specification, when the measured temperature and/or pressure affect the physical properties, unless otherwise specified, the corresponding physical properties refer to properties measured at room temperature and/or pressure.

The term room temperature is a natural temperature that is not heated or reduced, for example, any temperature within the range of about 10°C to 30°C, and may mean a temperature of about 25°C or 23°C. In addition, unless otherwise specified, the unit of temperature in the present specification is °C.

The term atmospheric pressure is the pressure when it is not particularly reduced or increased, and can usually be on the order of 1 atmosphere, such as atmospheric pressure.

This application relates to a curable composition. In one example, the curable composition may include a main material and a curing agent, and may be cured by mixing the main material and the curing agent.

The curable composition may be active energy ray curable, moisture curable, thermosetting, or room temperature curable, but is preferably room temperature curable. The term room temperature curability refers to a curable composition that can be cured in a state maintained at room temperature as mentioned above. Whether the curable composition is room temperature curable can be evaluated in the manner described in Examples below. For example, it can be seen that the curable composition evaluated as Pass in the evaluation of curability (room temperature curability) of the curable composition of Examples has room temperature curability.

The curable composition may be an adhesive composition. The term adhesive composition may refer to a composition designed to exhibit adhesion of a certain level or higher before or after curing.

The curable composition may be a one-component or two-component curable composition. The term one-component curable composition refers to a curable composition formed to be cured by itself without being mixed with other components, and the two-component curable composition refers to a curable composition formed to be cured only when mixed with other components. In general, the two-component curable composition is stored in a state in which the main material including the curable resin and the curing agent are separated, and for curing, the main material and the curing agent must be in contact. As used herein, the term “main material” means a curable resin or a composition containing the same in the separated two-component curable composition, and the curing agent refers to a curing agent or a composition containing the same in the separated two-component curable composition. can

The curable composition may be a curable composition used for manufacturing a battery module or a battery pack. As exemplarily described below, the curable composition is injected into the battery module case in certain disclosures of the present application and is in contact with one or more battery cells present in the battery module to fix the battery cells within the battery module. can be used

The curable composition may be designed to exhibit properties suitable for the use.

For example, the curable composition may exhibit an adhesive force of 200 gf/cm or more to a poly(ethylene terephthalate) (PET) film, or may be formulated to form a cured product exhibiting such adhesion. In general, like the curable composition of the present application, the epoxy-based curable composition exhibits low adhesion to the polyester-based material, but the curable composition of the present application may exhibit such high adhesion to the PET film, which is a representative polyester material. . The adhesive force may be measured in the manner described in Examples to be described later. In another example, the adhesion to the PET film is about 250 gf/cm or more, 300 gf/cm or more, 350 gf/cm or more, 400 gf/cm or more, 450 gf/cm or more, 500 gf/cm or more, 550 gf/cm or more. cm or more, 600 gf/cm or more, 650 gf/cm or more, 700 gf/cm or more, 750 gf/cm or more, or about 800 gf/cm or more. When the adhesive force satisfies the above range, appropriate impact resistance and vibration resistance can be ensured. The upper limit of the adhesive force of the resin layer is not particularly limited, and for example, about 1,000 gf/cm or less, 900 gf/cm or less, 800 gf/cm or less, 700 gf/cm or less, 600 gf/cm or less, or about 500 gf It may be less than /cm. If the adhesive force is too high, there is a risk of tearing the cured curable composition and the pouch portion to which it is attached. For example, if an impact occurs to the extent that the shape of the battery module is deformed due to an accident while driving, if the battery cell is attached too strongly through the cured curable composition layer, the pouch is torn and hazardous substances inside the battery are exposed or may explode.

In one example, the curable composition may exhibit excellent electrical insulation before and after curing. When the curable composition or a cured product thereof exhibits electrical insulation in the battery module structure described below, the performance of the battery module is maintained and stability can be secured. For example, the curable composition or a cured product thereof may exhibit a resistance of about 1 GΩ or more. The resistance is measured in the manner described in the Examples herein. In another example, the resistance is 1.5 GΩ or more, 2 GΩ or more, 2.5 GΩ or more, 3 GΩ or more, 3.5 GΩ or more, 4 GΩ or more, 4.5 GΩ or more, 5 GΩ or more, 5.5 GΩ or more, 6 GΩ or more, 6.5 GΩ or more , 7 GΩ or more, 7.5 GΩ or more, 8 GΩ or more, 8.5 GΩ or more, 9 GΩ or more, 9.5 GΩ or more, 10 GΩ or more, 10.5 GΩ or more, 11 GΩ or more, 11.5 GΩ or more, 12 GΩ or more, 12.5 GΩ or more, 13 It may be greater than or equal to GΩ, greater than 13.5 GΩ, greater than 14 GΩ, greater than 14.5 GΩ, greater than 15 GΩ, greater than 15.5 GΩ, greater than 16 GΩ, or greater than 16.5 GΩ, or less than or equal to 30 GΩ, less than or equal to 25 GΩ, or less than or equal to 20 GΩ.

The said curable composition or its hardened|cured material can show high thermal conductivity. For example, the curable composition or a cured product thereof may have a thermal conductivity of about 2 W/mK or more, 2.5 W/mK or more, 3 W/mK or more, 3.5 W/mK or more, or about 4 W/mK or more. The thermal conductivity is about 50 W/mK or less, 45 W/mk or less, 40 W/mk or less, 35 W/mk or less, 30 W/mk or less, 25 W/mk or less, 20 W/mk or less, 15 W/ mk or less, 10 W/mK or less, 5 W/mK or less, 4.5 W/mK or less, or about 4.0 W/mK or less. The thermal conductivity is, for example, a value measured according to ASTM D5470 standard or ISO 22007-2 standard, or a value measured according to a method disclosed in Examples of the present specification to be described later. Although the curable composition of the present application is an epoxy-based composition including a high content of thermally conductive filler as described below for achieving the thermal conductivity, nevertheless, as mentioned above, it will exhibit high adhesion to the PET film. can

The curable composition may include a curing agent for the main material and/or the main material (specifically, a curable resin contained in the main material). In one example, when the curable composition is of the two-component type, the main material and the curing agent may be physically separated so as not to contact each other, and in the case of the one-component type, the main material and the curing agent may be mixed with each other. In addition, in the present specification, the term curable resin refers to a compound that can become a resin after curing even if it is not in a state of being a resin by itself.

When the curable composition is a two-component type, the term curable composition herein refers to a curable composition including the main material and the curing agent in a separate state, or as a composition in a state in which the main material and the curing agent are mixed, The curable resin and the curing agent may be in a state in which they have reacted with each other, or may refer to a curable composition that is in a state before the reaction.

The main material is a curable resin, and may contain an epoxy compound of a specific epoxy equivalent. As used herein, the term epoxy equivalent is an equivalent (g/eq) for one epoxy group, as is known, and is a value obtained by dividing the average molecular weight of the epoxy compound by the number of epoxy groups per molecule. This epoxy equivalent can be measured according to a method known in the industry, for example, it can be confirmed by JIS K-7236 standard or KD-AS-001 method of Kukdo Chemical.

As used herein, the term epoxy group may mean a glycidyl group, a glycidyloxy group, or a so-called alicyclic epoxy group.

As the epoxy compound, an epoxy compound having an epoxy equivalent of about 200 g/eq or more can be used. As the epoxy compound, by applying an epoxy equivalent of 200 g/eq or more, it is possible to provide a curable composition or a cured product thereof having excellent adhesion (especially, adhesion to a polyester material). In another example, the epoxy equivalent is about 210 g/eq or more, about 220 g/eq or more, about 230 g/eq or more, about 240 g/eq or more, about 250 g/eq or more, about 260 g/eq or more, about 270 g/eq or more, about 280 g/eq or more, about 290 g/eq or more, about 300 g/eq or more, about 310 g/eq or more, about 320 g/eq or more, about 330 g/eq or more, about 340 It may be about g/eq or more or 350 g/eq or more. The upper limit of the epoxy equivalent is not particularly limited, but, for example, the epoxy equivalent may be determined to be about 600 g/eq or less, 550 g/eq or less, or 500 g/eq or less.

As the epoxy compound, an epoxy compound having a conversion rate of 20 or more may be used. By applying an epoxy compound having a conversion rate of 20 or more, it is possible to maintain excellent adhesion (especially, adhesion to a polyester material). Although the upper limit of the conversion rate is not limited, the conversion rate may be determined in a range of about 60 or less in consideration of a reaction rate or thermal conductivity of a curable composition or a cured product thereof.

The epoxy compound may have a viscosity of about 350 cps or more. In another example, the viscosity may be about 400 cps or more, 450 cps or more, 500 cps or more, 550 cps or more, 600 cps or more, 650 cps or more, 700 cps or more, 850 cps or more, or 900 cps or more. The upper limit of the viscosity is not particularly limited, but, for example, the viscosity of the epoxy compound may be about 13,000 cps or less, 12,000 cps or less, 1,100 cps or less, 1,000 cps or less, or 900 cps or less. The viscosity is the viscosity at 25 ℃ measured by the KD-AS-005 method provided by Kukdo Chemical.

As the epoxy compound, various types may be used as long as the above-mentioned physical properties are satisfied. In order to secure appropriate physical properties, a hydrophobic epoxy compound may be used as the epoxy compound. Epoxy compounds are mostly known to be hydrophobic, but it may be appropriate to select, for example, an epoxy compound known as an epoxy compound, a so-called dimer acid modified epoxy resin or a rubber modified epoxy resin. can Such an epoxy compound can effectively satisfy the desired physical properties. As the above compound, for example, YD-172X75, YD-172, or YD-171 manufactured by Kukdo Chemical Company, or KR 208 product may be applied, but is not limited thereto.

The proportion of the epoxy compound having an epoxy equivalent of 200 g/eq or more may be in the range of greater than about 20% by weight to less than 60% by weight. The ratio of the epoxy compound may be a ratio when the ratio of the total epoxy compound present in the curable composition or the main material is 100% by weight. For example, when the main material contains an epoxy compound having an epoxy equivalent of 200 g / eq or more, a polyfunctional epoxy diluent and a second epoxy compound to be described later, the ratio is an epoxy compound having an epoxy equivalent of 200 g / eq or more, It may be a ratio when the total weight of a functional epoxy diluent and a 2nd epoxy compound is 100 weight%. The above is an example. That is, when the curable composition or main material contains only any two of an epoxy compound having an epoxy equivalent of 200 g/eq or more, a polyfunctional epoxy diluent, and a second epoxy compound as an epoxy compound, the sum of the two epoxy compounds is 100 weight The ratio is calculated as a percentage, and if another epoxy compound is included in the main material or the curable composition in addition to the two or three epoxy compounds, the ratio can be calculated by taking the total epoxy compound as 100% by weight. In another example, the ratio is about 21 wt% or more, 22 wt% or more, 23 wt% or more, 24 wt% or more, 25 wt% or more, 26 wt% or more, 27 wt% or more, 28 wt% or more, 29 wt% or more. or more, 30% or more, 31% or more, 32% or more, 33% or more, 34% or more, 35% or more, 36% or more, 37% or more, 38% or more, 39% or more or more, 40% or more, 41% or more, or 42% or more, or 58% or less, 57% or less, 56% or less, 55% or less, 54% or less, 53% or less, 52% or less % or less, 51% or less, 50% or less, 49% or less, 48% or less, 47% or less, 46% or less, 45% or less, 44% or less, 43% or less, 42% or less % or less, 41% or less, 40% or less, 39% or less, 38% or less, 37% or less, 36% or less, 35% or less, 34% or less, 33% or less, 32% or less % or less, 31 wt% or less, 30 wt% or less, 29 wt% or less, 28 wt% or less, 27 wt% or less, 26 wt% or less, or 25 wt% or less.

The subject matter may also contain a polyfunctional epoxy diluent as an additional component. The epoxy diluent means a compound having a sufficiently low viscosity to dilute a component included in the main material, and including at least two or more epoxy groups. The polyfunctional epoxy diluent is, in one example, contains 2 or more or 3 or more epoxy groups, or 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less It may contain up to 3 epoxy groups.

As the polyfunctional epoxy diluent, an epoxy diluent having an epoxy equivalent of about 50 g/eq or more may be used. Through this, it is possible to more effectively provide a curable composition having desired physical properties. The epoxy equivalent weight is in another example about 60 g/eq or more, about 70 g/eq or more, about 80 g/eq or more, about 90 g/eq or more, about 100 g/eq or more, about 110 g/eq or more, about It may be about 120 g/eq or more or 130 g/eq or more. The upper limit of the epoxy equivalent is not particularly limited, but for example, about 200 g/eq or less, 190 g/eq or less, 180 g/eq or less, 170 g/eq or less, 160 g/eq or less, or 155 g/eq or less The epoxy equivalent may be determined below.

The epoxy diluent may have a viscosity of about 350 cps or less. In another example, the viscosity is about 50 cps or more, 55 cps or more, 60 cps or more, 65 cps or more, 70 cps or more, 75 cps or more, 80 cps or more, 85 cps or more, 90 cps or more, 95 cps or more, or 100 cps or more. It may be to some extent The viscosity is the viscosity at 25 ℃ measured by the KD-AS-005 method provided by Kukdo Chemical.

As the epoxy diluent, various types may be used as long as the above-mentioned physical properties are satisfied. In order to secure appropriate physical properties, an aliphatic epoxy diluent may be used as the epoxy diluent. For example, an aliphatic hydrocarbon compound substituted with two or more glycidyloxy groups may be applied as the epoxy diluent. In the above, the hydrocarbon compound is a compound composed of a carbon atom and a hydrogen atom, and two or more of the hydrogen atoms of the compound are substituted with the glycidyloxy group. Examples of the hydrocarbon compound include, but are not limited to, an alkane, an alkene, or an alkyne. The hydrocarbon compound is in one example 1 to 20, 2 to 20, 3 to 20, 4 to 20, 5 to 20, 6 to 20, 6 to 16, 6 from 12 to 12 or from 6 to 8 carbon atoms. The number of carbon atoms is the number of carbon atoms excluding carbon atoms included in the glycidyloxy group. In addition, in any case, the hydrocarbon compound may be substituted with a group other than the glycidyloxy group. The number of glycidyloxy groups substituted in the hydrocarbon compound is 3 or more, or 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less in another example It may be three or less. The diluent may be, for example, YH-300 or LD-223 manufactured by Kukdo Chemical, but is not limited thereto.

The ratio of the epoxy diluent may be in the range of about 15 to 400 parts by weight relative to 100 parts by weight of the epoxy compound having an epoxy equivalent of 200 g/eq or more. In another example, the ratio is 20 parts by weight or more or 25 parts by weight or more, 390 parts by weight or less, 380 parts by weight or less, 370 parts by weight or less, 360 parts by weight or less, 350 parts by weight or less, 340 parts by weight or less, 330 parts by weight or less Hereinafter, the amount may be about 320 parts by weight or less, 310 parts by weight or less, or 300 parts by weight or less. Under such a ratio, it is possible to provide effectively that the desired properties are adequately secured.

The curable composition or the main material is an epoxy compound different from the above-described epoxy compound, and may further include, for example, an aromatic epoxy compound or a rubber-modified epoxy compound. When the aromatic epoxy compound or rubber-modified epoxy resin is additionally included for differentiation, this compound may be referred to as a second epoxy compound, and in this case, the epoxy equivalent weight is 200 g/eq The above epoxy compound may be referred to as a first epoxy compound. However, the second epoxy compound is an optional component. Such a second epoxy compound can usually contribute to the insulation of the curable composition or its cured product.

As the second epoxy compound, a compound having an epoxy equivalent of about 50 g/eq or more may be used. The epoxy equivalent weight is in another example about 60 g/eq or more, about 70 g/eq or more, about 80 g/eq or more, about 90 g/eq or more, about 100 g/eq or more, about 110 g/eq or more, about At least 120 g/eq, at least about 130 g/eq, at least about 140 g/eq, at least about 150 g/eq, at least about 160 g/eq, at least about 170 g/eq, at least about 180 g/eq, at least about 190 It may be about g/eq or more, about 200 g/eq or more, or about 210 g/eq or more. The upper limit of the epoxy equivalent is not particularly limited, but for example, about 300 g/eq or less, 290 g/eq or less, 280 g/eq or less, 270 g/eq or less, 260 g/eq or less, 250 g/eq or less The epoxy equivalent may be determined to be 240 g/eq or less, 230 g/eq or less, 220 g/eq or less, 210 g/eq or less, 200 g/eq or less, or 190 g/eq or less.

The specific kind of the second epoxy compound that can be applied is not particularly limited. For example, as the aromatic epoxy compound, a so-called bisphenol A-type epoxy compound (or resin) or a bisphenol F-type epoxy compound (or resin) may be used, and as such a compound, for example, YDF of Kukdo Chemical -175 products can be exemplified. In addition, as the rubber-modified epoxy compound (or resin), for example, Kukdo Chemical's KR-628 product may be used.

In one example, as the aromatic epoxy compound (or resin), an epoxy compound having a viscosity of about 1,000 cps to 6,000 cps may be used, and as a rubber-modified epoxy compound (or resin), the viscosity is about 35,000 cps to 65,000 cps level Epoxy compounds may be applied, but are not limited thereto. The viscosity is the viscosity at 25 ℃ measured by the KD-AS-005 method provided by Kukdo Chemical.

The second epoxy compound may be included in a ratio of about 250 parts by weight or less relative to 100 parts by weight of the first epoxy compound in the curable composition or the main material. In another example, the ratio is 0 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, or 230 parts by weight or less, 210 parts by weight or less, 190 parts by weight or less. It may be about 170 parts by weight or less, 150 parts by weight or less, 130 parts by weight or less, or 110 parts by weight or less.

The curable composition or curing agent may also include a mixture of a phenolic compound and an amine compound. The mixture may act as a curing agent, for example curing the epoxy compound of the substrate. As a compound acting as a curing agent, by applying such a mixture as above, it is possible to provide a curable composition as an object of the present application.

The phenolic compound is not particularly limited, but a so-called styrenated phenol compound may be used in view of providing a curable composition having desired properties. The styrenated phenol compound includes a compound known in the art as a styrenated phenol or a derivative thereof, for example, mono alpha-methylstyrenated phenol (MSP), di alpha-methylstyrenated phenol. Renated phenol (di-alpha-methylstyrenated phenol, DSP) and/or tri-alpha-methylstyrenated phenol (TSP) or the like or derivatives thereof may be applied.

On the other hand, the phenol compound is not particularly limited, but a so-called ethylene amine compound may be used from the viewpoint of providing a curable composition having desired properties. Such an ethylene amine compound is known in the art as a compound in which an ethylene bond exists between amine functional groups. Examples of applicable ethylene amine compounds include ethylene diamine, diethylenetriamine, aminoethyl piperazine, triethylenetetraamine, tri(2-aminoethyl)amine, N,N'-bis(2-aminoethyl)pipeline razine, piperazine ethylethylenediamine and/or tetraethylenepentaamine, and have a ring structure such as aminoethyl piperazine, N,N'-bis(2-aminoethyl)piperazine and/or piperazine ethylethylenediamine. Ethylene amine compounds including, but not limited to, may be applied.

The mixture may contain 15 to 60 parts by weight of the phenol compound based on 100 parts by weight of the amine compound. In another example, the ratio may be 20 parts by weight or more or 25 parts by weight or more, or about 55 parts by weight or less, 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, or 35 parts by weight or less. Under such a ratio, it is possible to more effectively provide a curable composition having desired physical properties.

By applying such a mixture as a curing agent, it is possible to provide a curable composition or curing agent in which desired physical properties are secured.

As the mixture of the phenol compound and the amine compound, it is advantageous to apply a liquid mixture at room temperature. The liquid phase at room temperature may be effective in securing the desired physical properties compared to the solid phase at room temperature.

As a mixture of such a phenol compound and an amine compound, KH-1502, KH-1503, or KH-1502-2 products manufactured by Kukdo Chemical are known, but the mixture applicable in the present application is not limited thereto.

The mixture of the phenol compound and the amine compound may be included in the curable composition in a ratio of 10 to 300 parts by weight relative to 100 parts by weight of the first epoxy compound (epoxy compound having an epoxy equivalent of 200 g/eq or more). In another example, the ratio is about 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, 90 parts by weight or more, 100 parts by weight or more. or more, 110 parts by weight or more, 120 parts by weight or more, or 130 parts by weight or more, 290 parts by weight or less, 280 parts by weight or less, 260 parts by weight or less, 250 parts by weight or less, or 240 parts by weight or less.

In the case of the two-component composition, the ratio of the mixture of the phenol compound and the amine compound in the curing agent may be about 10 to 100% by weight. In another example, the ratio may be 20 wt% or more, 30 wt% or more, 40 wt% or more, 50 wt% or more, or 60 wt% or more, or 90 wt% or less, 80 wt% or less, or 70 wt% or less.

The curable composition or curing agent may also include an additional component for adjusting the viscosity of the mixture. As such a component, a compound capable of reacting with the main epoxy compound may be applied.

As such a compound, for example, an amide compound, an ether amine compound, or a thiol compound may be exemplified, but is not limited thereto.

The compounds may be included, for example, in an amount of 150 parts by weight or less based on 100 parts by weight of the mixture of the phenol compound and the amine compound. The ratio may be about 0 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, or 40 parts by weight or more in another example, and in another example about 140, 130 parts by weight or less, 120 parts by weight or less, It may be about 110 parts by weight or less, 100 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less, or 60 parts by weight or less.

The curable composition may also contain various kinds of other components as long as the above-described components are basically included.

For example, the curable composition may further include a filler component known as a so-called thermally conductive filler. The term thermally conductive filler may refer to a filler known to have a thermal conductivity of at least about 1 W/mK, at least 5 W/mK, at least 10 W/mK, or at least about 15 W/mK. The thermal conductivity of the thermally conductive filler may be about 400 W/mK or less, 350 W/mK or less, or about 300 W/mK or less. The type of the thermally conductive filler is not particularly limited, but an inorganic filler, for example, a ceramic filler, may be applied when insulating properties are taken into consideration. For example, ceramic particles such as alumina, aluminum nitride (AlN), boron nitride (BN), silicon nitride, SiC or BeO may be used. In addition to the above, various types of fillers may be used. For example, in order to secure the insulating properties of the resin layer in which the curable composition is cured, the use of a carbon filler such as graphite may be considered. Alternatively, fillers such as, for example, fumed silica, clay or calcium carbonate may be used.

The filler may be included in a very large amount in the curable composition. For example, the filler is about 50 parts by weight or more, about 100 parts by weight or more, about 150 parts by weight or more, about 200 parts by weight or more, about 250 parts by weight or more, about 300 parts by weight based on 100 parts by weight of the main material and/or curing agent. parts by weight or more, about 350 parts by weight or more, about 400 parts by weight or more, about 450 parts by weight or more, about 500 parts by weight or more, about 550 parts by weight or more, about 600 parts by weight or more, about 650 parts by weight or more, about 700 parts by weight or more , may be used in a ratio of about 750 parts by weight or more, about 800 parts by weight or more, 820 parts by weight or more, or about 840 parts by weight or more. The filler may be used in an amount of about, 2,000 parts by weight or less, 1,800 parts by weight or less, or about 1,6000 parts by weight or less, based on 100 parts by weight of the main material and/or curing agent. In addition, in the case of a two-component curable composition, the filler may be included in the main material and/or the curing agent.

In order to effectively maintain viscosity characteristics and the like even by applying an excessive amount of filler and to more effectively use desired thermal conductivity, insulation, etc., as the filler, at least three kinds of fillers having different average particle diameters may be applied.

For example, the thermally conductive filler includes a first inorganic filler having an average particle diameter in a range of about 1 μm to about 3 μm, a second inorganic filler having an average particle diameter in a range of about 15 μm to about 25 μm, and an average particle diameter of about and at least a third inorganic filler in the range of 35 μm to about 200 μm. The average particle diameter of the filler means a D50 particle diameter among the aforementioned particle diameters. In this case, when the total weight of the fillers is 100 parts by weight, the first inorganic filler is included in about 15 to about 35 parts by weight or about 20 to about 30 parts by weight, and the second inorganic filler is about 25 to about 45 parts by weight. Alternatively, it may be included in an amount of about 30 to about 40 parts by weight, and the third inorganic filler may be included in an amount of about 30 to about 50 parts by weight or about 35 to about 45 parts by weight.

By applying the three types of fillers having the above particle diameters in the above ratio, it is possible to provide a curable composition in which handling properties are secured by exhibiting appropriate viscosity even when a high content filler is filled.

The shape of the inorganic filler is not particularly limited and may be selected in consideration of the viscosity and thixotropy of the curable composition, the possibility of sedimentation in the curable composition, thermal conductivity, insulation, filling effect or dispersibility, and the like. For example, it is advantageous to use a spherical inorganic filler in consideration of the amount to be filled, but in consideration of network formation, conductivity, and thixotropy, non-spherical inorganic fillers, for example, Inorganic fillers may also be used.

In the present application, the term spherical particle means a particle having a sphericity of about 0.95 or more, and a non-spherical particle means a particle having a sphericity of less than 0.95. The sphericity can be confirmed through particle shape analysis.

In one example, all spherical fillers, ie, fillers having a sphericity of 0.95 or more, may be used as the first to third inorganic fillers in consideration of the above-described filling effect. In another example, at least one of the first to third inorganic fillers may be a non-spherical filler having a sphericity of less than 0.95.

The curable composition, the main material and/or the curing agent may include other known additives in addition to the above components. Examples of such additives include, but are not limited to, viscosity modifiers, diluents, dispersants, surface treatment agents, catalysts, and/or coupling agents.

The dispersant is not particularly limited, and a compound type, nonionic, anionic or cationic dispersant may be used, and a fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactant may also be used. In one example, as the dispersing agent, a cationic dispersing agent having a phosphoric acid group or a phosphorous acid group may be used. The dispersant may be used in an amount of 0.01 parts by weight to 0.5 parts by weight based on 100 parts by weight of the main material and/or curing agent.

As the flame retardant, a phosphorus-based flame retardant may be applied, and a liquid flame retardant or a solid flame retardant or a semi-solid flame retardant at room temperature may be used. The liquid phosphorus-based flame retardant is a flame retardant exhibiting a liquid phase at room temperature, and the melting point may be less than room temperature, for example, less than about 30 ° C., less than 25 ° C., less than 20 ° C., less than 15 ° C., less than 10 ° C. It may be a flame retardant. As an example of the liquid phosphorus-based flame retardant, a phosphite-based flame retardant such as resorcinol bis (diphenyl phosphate) may be used. The liquid phosphorus-based flame retardant may include about 5 parts by weight to 25 parts by weight based on 100 parts by weight of the total resin content.

Diluents or dispersants are generally used to lower the viscosity of the curable composition, and various types known in the art may be used without limitation as long as they can exhibit the above action.

The surface treatment agent is for surface treatment of the filler, and as long as it can exhibit the above action, various types of known in the art may be used without limitation.

The coupling agent, for example, may be used to improve the dispersibility of the thermally conductive filler such as alumina, and as long as it can exhibit the above action, various types of known in the art may be used without limitation.

A method of preparing the curable composition as described above is not particularly limited, and, for example, may be prepared by mixing each of the above-described components with an appropriate mixer or the like.

The present application also relates to a battery module. The module includes a module case and a battery cell. The battery cell may be accommodated in the module case. One or more battery cells may be present in the module case, and a plurality of battery cells may be accommodated in the module case. The number of battery cells accommodated in the module case is not particularly limited as it is adjusted according to the use or the like. The battery cells accommodated in the module case may be electrically connected to each other.

The module case may include at least a side wall and a lower plate forming an internal space in which the battery cell can be accommodated. In addition, the module case may further include an upper plate for sealing the inner space. The side wall, the lower plate, and the upper plate may be integrally formed with each other, or the module case may be formed by assembling the separate side walls, the lower plate, and/or the upper plate, respectively. The shape and size of the module case are not particularly limited, and may be appropriately selected depending on the purpose or the shape and number of battery cells accommodated in the inner space.

In the above, the terms upper plate and lower plate are terms of a relative concept used to distinguish between at least two plates constituting the module case. That is, it does not mean that the upper plate necessarily exists in the upper part and the lower plate necessarily exists in the lower part in an actual use state.

1 is a view showing an exemplary module case 10, and is an example of a box-shaped case 10 including one lower plate 10a and four side walls 10b. The module case 10 may further include an upper plate 10c for sealing the inner space.

FIG. 2 is a schematic view of the module case 10 of FIG. 2 in which the battery cells 20 are accommodated, as viewed from above.

A hole may be formed in the lower plate, the side wall, and/or the upper plate of the module case. The hole may be an injection hole used to inject a material for forming the resin layer, that is, a two-component curable composition, when the resin layer is formed by an injection process. The shape, number, and position of the holes may be adjusted in consideration of injection efficiency of the resin layer forming material. In one example, the hole may be formed in at least the lower plate and/or the upper plate.

In one example, the hole may be formed at about 1/4 to 3/4 of the total length of the side wall, the lower plate, or the upper plate, or about 3/8 to 7/8, or approximately in the middle. By injecting the two-component curable composition through the injection hole formed at this point, the resin layer can be injected so as to have a wide contact surface. The 1/4, 3/4, 3/8 or 7/8 point is, for example, as shown in FIG. 3, the total length (L) measured based on the end face (E) of any one of the lower plate or the like. ), the ratio of the distance (A) to the formation location of the hole. In addition, the end (E) at which the length (L) and the distance (A) are formed may be any end (E) as long as the length (L) and the distance (A) are measured from the same end (E). there is. In FIG. 3, the injection hole 50a is positioned approximately in the middle of the lower plate 10a.

The size and shape of the injection hole are not particularly limited, and may be adjusted in consideration of injection efficiency of the resin layer material, which will be described later. For example, the hole may have a polygonal or amorphous shape such as a circle, an ellipse, a triangle or a square. The number and spacing of the injection holes are not particularly limited, and as described above, the resin layer may be adjusted to have a large contact area with the lower plate and the like.

An observation hole (eg, ( 50b ) in FIG. 3 ) may be formed at the ends of the upper plate and the lower plate in which the injection hole is formed. This observation hole, for example, when injecting the resin layer material through the injection hole, may be formed to observe whether the injected material is well injected to the end of the side wall, the lower plate or the upper plate. The position, shape, size, and number of the observation hole are not particularly limited as long as they are formed so as to confirm whether the injected material is properly injected.

The module case may be a thermally conductive case. The term thermally conductive case refers to a case having an overall thermal conductivity of 10 W/mk or more, or at least including a portion having the above-described thermal conductivity. For example, at least one of the aforementioned sidewall, lower plate, and upper plate may have the aforementioned thermal conductivity. In another example, at least one of the side wall, the lower plate, and the upper plate may include a portion having the thermal conductivity. For example, the battery module of the present application may include a first filler-containing cured resin layer in contact with the upper plate and the battery cell, and a second filler-containing cured resin layer in contact with the lower plate and the battery cell. The cured resin layer containing two fillers may be a thermally conductive resin layer, and thus at least the lower plate may have thermal conductivity or may include a thermally conductive portion.

The thermal conductivity of the thermally conductive upper plate, lower plate, sidewall, or thermally conductive portion is, in another example, about 20 W/mk or more, 30 W/mk or more, 40 W/mk or more, 50 W/mk or more, 60 W /mk or more, 70 W/mk or more, 80 W/mk or more, 90 W/mk or more, 100 W/mk or more, 110 W/mk or more, 120 W/mk or more, 130 W/mk or more, 140 W/mk or more or more, 150 W/mk or more, 160 W/mk or more, 170 W/mk or more, 180 W/mk or more, 190 W/mk or more, or about 195 W/mk or more. The higher the thermal conductivity, the more advantageous in terms of heat dissipation characteristics of the module, and the upper limit thereof is not particularly limited. In one example, the thermal conductivity is about 1,000 W/mK or less, 900 W/mk or less, 800 W/mk or less, 700 W/mk or less, 600 W/mk or less, 500 W/mk or less, 400 W/mk or less, 300 W/mk or about 250 W/mK or less, but is not limited thereto. The type of material exhibiting the above-described thermal conductivity is not particularly limited, and for example, a metal material such as aluminum, gold, silver, tungsten, copper, nickel, or platinum may be used. The module case may be entirely made of the thermally conductive material as described above, or at least a portion of the module case may be made of the thermally conductive material. Accordingly, the module case may have thermal conductivity within the above-mentioned range or may include at least one portion having the above-mentioned thermal conductivity.

In the module case, a portion having thermal conductivity within the above range may be a portion in contact with the resin layer and/or the insulating layer. In addition, the portion having the thermal conductivity may be a portion in contact with a cooling medium such as cooling water. In the case of having such a structure, heat generated from the battery cell can be effectively dissipated to the outside.

In the present application, the term battery cell refers to a single unit secondary battery including an electrode assembly and an exterior material.

The type of battery cell accommodated in the battery module case is not particularly limited, and all known various battery cells may be applied. In one example, the battery cell may be of a pouch type.

In particular, in the present application, as the battery cell, a battery cell whose outermost layer is a polyester layer (eg, a PET layer) may be applied.

The battery module of the present application may further include a resin layer. Specifically, the battery module of the present application may include a cured resin layer in which the filler-containing composition is cured. The cured resin layer may be formed from the above-described two-component curable composition.

The battery module may include, as the resin layer, a first cured resin layer in contact with the upper plate and the battery cell, and a second cured resin layer in contact with the lower plate and the battery cell. At least one of the first and second cured resin layers may include a cured product of the curable composition described above, and thus may have the predetermined adhesive strength, thermal conductivity, room temperature curability and insulation properties described above.

In addition, the first and second cured resin layers may be thermally conductive resin layers. In this case, the thermal conductivity of the thermally conductive resin layer may be about 1.5 W/mK or more, 2 W/mK or more, 2.5 W/mK or more, 3 W/mK or more, 3.5 W/mK or more, or about 4 W/mK or more. . The thermal conductivity is about 50 W/mK or less, 45 W/mk or less, 40 W/mk or less, 35 W/mk or less, 30 W/mk or less, 25 W/mk or less, 20 W/mk or less, 15 W/ mk or less, 10 W/mK or less, 5 W/mK or less, 4.5 W/mK or less, or about 4.0 W/mK or less. When the resin layer is a thermally conductive resin layer as described above, the lower plate, the upper plate, and/or the sidewall to which the resin layer is attached may be a region having the aforementioned thermal conductivity of 10 W/mK or more. In this case, the portion of the module case showing the thermal conductivity may be a portion in contact with a cooling medium, for example, cooling water.

In addition, the resin layer may be a flame retardant resin layer. In the present application, the term flame retardant resin layer may mean a resin layer showing a V-0 grade in UL 94 V Test (Vertical Burning Test). This ensures safety against fires and other accidents that may occur in the battery module.

In the battery module of the present application, at least one of the sidewall, the lower plate, and the upper plate in contact with the resin layer may be the aforementioned thermally conductive sidewall, lower plate, or upper plate. Meanwhile, in the present specification, the term contact means, for example, that the resin layer and the upper plate, lower plate and/or sidewall or battery cell are in direct contact, or other elements, for example, an insulating layer, etc. exist between them. It could mean the case. In addition, the resin layer in contact with the thermally conductive sidewall, the lower plate, or the upper plate may be in thermal contact with the object. At this time, in the thermal contact, the resin layer is in direct contact with the lower plate or the like, or another element, for example, an insulating layer to be described later, exists between the resin layer and the lower plate, etc., but the other element is the It may mean a state in which heat transfer from the battery cell to the resin layer and from the resin layer to the lower plate is not prevented. In the above, the fact that the heat transfer is not hindered means that even when another element (eg, an insulating layer or a guiding part to be described later) exists between the resin layer and the lower plate, the total thermal conductivity of the other element and the resin layer. is about 1.5 W/mK or more, 2 W/mK or more, 2.5 W/mK or more, 3 W/mK or more, 3.5 W/mK or more, or about 4 W/mK or more, or is in contact with the resin layer and its It means that the total thermal conductivity of the lower plate is included within the above range even if the other elements are present. The thermal conductivity of the thermal contact is about 50 W/mK or less, 45 W/mk or less, 40 W/mk or less, 35 W/mk or less, 30 W/mk or less, 25 W/mk or less, 20 W/mk or less, 15 W/mk or less, 10 W/mK or less, 5 W/mK or less, 4.5 W/mK or less, or about 4.0 W/mK or less. Such thermal contact may be achieved by controlling the thermal conductivity and/or thickness of the other element, if present.

The thermally conductive resin layer may be in thermal contact with the lower plate and the like, and may also be in thermal contact with the battery cell. Through the adoption of the above structure, the heat dissipation characteristics are ensured, and the unit volume while significantly reducing the various fastening parts or cooling equipment of the module, etc., which were previously required when configuring a general battery module or a battery pack, which is an aggregate of such modules. It is possible to implement a module in which more battery cells are accommodated per unit. Accordingly, in the present application, it is possible to provide a more compact, light and high-output battery module.

4 is an exemplary cross-sectional view of the battery module. In Figure 4, the module, the case 10 including a side wall (10b) and a lower plate (10a); It may be of a form including a plurality of battery cells 20 housed in the inside of the case and the resin layer 30 in contact with both the battery cells 20 and the case 10 . Although FIG. 4 is a view of the resin layer 30 present on the lower plate 10a side, the battery module of the present application may include a resin layer positioned on the upper plate side in the same manner as in FIG. 4 .

In the structure, the lower plate in contact with the resin layer 30 may be a thermally conductive lower plate as described above.

The contact area between the resin layer and the lower plate may be about 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or about 95% or more of the total area of the lower plate or the like. The upper limit of the contact area is not particularly limited, and for example, may be 100% or less or less than about 100%.

When the upper plate or lower plate is thermally conductive and the cured resin layer in contact with it is also thermally conductive, the thermally conductive portion or the thermally conductive lower plate may be a portion in contact with a cooling medium such as cooling water. That is, as schematically shown in FIG. 4, heat (H) can be easily discharged to the lower plate by the above structure, and by contacting the lower plate and the like with the cooling medium (CW), even in a more simplified structure Dissipation of heat can be facilitated.

Each of the resin layers may have a thickness, for example, in a range of about 100 μm to about 5 mm or in a range of about 200 μm to about 5 mm. In the structure of the present application, the thickness of the resin layer may be set to an appropriate thickness in consideration of a desired heat dissipation characteristic or durability. The thickness may be the thickness of the thinnest part of the resin layer, the thickness of the thickest part, or the average thickness.

As shown in FIG. 4, at least one surface of the inside of the module case 10, for example, a surface 10a in contact with the resin layer 30, has a guiding part ( 10d) may be present. In this case, the shape of the guiding part 10d is not particularly limited, and an appropriate shape may be adopted in consideration of the shape of the applied battery cell. The guiding portion 10d may be formed integrally with the lower plate or the like, or may be attached separately. The guiding part 10d may be formed using a thermally conductive material, for example, a metal material such as aluminum, gold, silver, tungsten, copper, nickel, or platinum in consideration of the above-described thermal contact. In addition, although not shown in the drawings, an interleaving paper or an adhesive layer may exist between the battery cells 20 to be accommodated. In the above, the interleaf may serve as a buffer during charging and discharging of the battery cell.

In one example, the battery module may further include an insulating layer between the module case and the battery cell or between the resin layer and the module case. 5 exemplarily illustrates a case in which the insulating layer 40 is formed between the guiding portion 10d formed on the lower plate 10a of the case and the resin layer 30 . By adding an insulating layer, it is possible to prevent problems such as electric short circuit or fire caused by contact between the cell and the case due to an impact that may occur during use. The insulating layer may be formed using an insulating sheet having high insulating properties and thermal conductivity, or may be formed by coating or injecting an insulating material. For example, a process of forming an insulating layer may be performed before injection of the two-part curable composition. A so-called TIM (thermal interface material) or the like may be applied to the formation of the insulating layer. Alternatively, the insulating layer may be formed of an adhesive material. For example, the insulating layer may be formed using a resin layer with little or no filler such as a thermally conductive filler. As a resin component that can be used to form the insulating layer, acrylic resin, olefin resin such as PVC (poly(vinyl chloride)), PE (polyethylene), epoxy resin, silicone, or EPDM rubber ((ethylene propylene diene monomer rubber) The insulating layer may have a breakdown voltage of about 5 kV/mm or more, 10 kV/mm or more, 15 kV/mm measured according to ASTM D149, but is not limited thereto. or more, it may be 20 kV/mm or more, 25 kV/mm or more, or about 30 kV/mm or more.The breakdown voltage is not particularly limited as it shows excellent insulation as the value increases. For example, the insulation The dielectric breakdown voltage of the layer may be about 100 kV/mm or less, 90 kV/mm or less, 80 kV/mm or less, 70 kV/mm or less, or about 60 kV/mm or less. It can be set in an appropriate range in consideration of insulation or thermal conductivity, for example, about 5 μm or more, 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 60 μm or more, 70 μm or more. or more, 80 μm or more, or about 90 μm or more, and the upper limit of the thickness is not particularly limited, for example, about 1 mm or less, 200 μm or less, 190 μm or less, 180 μm or less, 170 μm or less , 160 μm or less or about 150 μm or less.

The present application also relates to a battery pack, for example, a battery pack including two or more of the aforementioned battery modules. In the battery pack, the battery modules may be electrically connected to each other. A method of configuring a battery pack by electrically connecting two or more battery modules is not particularly limited, and any known method may be applied.

The present application also relates to a device comprising the battery module or the battery pack. Examples of the device include, but are not limited to, a vehicle such as an electric vehicle, and may include any application requiring a secondary battery as an output. For example, a method of configuring the vehicle using the battery pack is not particularly limited, and a general method may be applied.

The present application may provide a curable composition excellent in one or more or all properties selected from adhesion, insulation, curability and thermal conductivity, or use of such a curable composition or cured product.

1 shows an exemplary module case that can be applied in the present application.
2 schematically shows a form in which a battery cell is accommodated in a module case.
3 schematically shows an exemplary lower plate having an injection hole and an observation hole formed therein.
4 and 5 schematically show the structure of an exemplary battery module.

Hereinafter, the present application will be described in detail through Examples, but the scope of the present application is not limited by the Examples below.

1. Evaluation of Adhesion

The lower plate of the aluminum module case on which the insulating film (poly(ethylene terephthalate)-based insulating layer) is formed and the PET (poly(ethylene terephthalate)) film were attached to each other using a curable composition. The width of attachment when attaching is about 10 mm The thickness of the cured layer (adhesive layer) of the curable composition was about 1 mm.The attachment is carried out by loading the curable composition between the insulating film and the PET film and then curing it. , while peeling the lower plate from the PET film at a speed of about 300 mm/min and a peeling angle of 180 degrees, the adhesive force is measured.

When the adhesive force confirmed in this way was 200 gf/cm or more, the numerical value was described, and when it was less than 200 gf/cm, it was described as NG.

2. Insulation (resistance) evaluation

The dielectric breakdown resistance was measured by applying a voltage of 0.5 kV for 60 seconds using a measuring device (HIPOT chroma 19052). The measurement was performed on a specimen in which a cured material layer (adhesive layer) of the curable composition was formed to a thickness of about 1 mm between two copper conductive tapes (Cu Tape) having a width and length of 10 mm and 20 mm, respectively. The dielectric breakdown resistance was measured according to the equipment and measurement conditions.

3. Thermal conductivity evaluation

Thermal conductivity was measured according to ASTM D5470 standard. After placing a resin layer (hardened material layer of a curable composition) between two copper bars according to the standard of ASTM D 5470, one of the two copper bars is in contact with a heater, and the other is a cooler ) was brought into contact with The heater was maintained at a constant temperature, and the capacity of the cooler was adjusted to create a thermal equilibrium state (a state showing a temperature change of about 0.1° C. or less in 5 minutes). The temperature of each copper rod was measured in a thermal equilibrium state, and thermal conductivity (K, unit: W/mK) was evaluated according to the following formula. When evaluating the thermal conductivity, the pressure applied to the resin layer was adjusted to be about 11 Kg/25 cm ² , and when the thickness of the resin layer was changed during the measurement process, the thermal conductivity was calculated based on the final thickness.

<Thermal conductivity formula>

K = (QХdx)/(AХdT)

In the above formula, K is the thermal conductivity (W/mK), Q is the heat moved per unit time (unit: W), dx is the thickness of the resin layer (unit: m), and A is the cross-sectional area of the resin layer (unit: m ² ), and dT is the temperature difference (unit: K) of the copper rod.

If the thermal conductivity confirmed as described above was 3 W/mK or more, it was evaluated as Pass, and if it was less than 3 W/mK, it was evaluated as NG.

Example 1.

Specific details of the components applied in the preparation of the curable composition are summarized below. A two-component curable composition was prepared by mixing the main material component and the curing agent component summarized below to prepare the main material and the curing agent, respectively. As the thermally conductive filler in each main material and curing agent, a mixture of alumina fillers having an average particle diameter (D50) of approximately 2 μm, 20 μm, and 70 μm was used. did That is, in the case of the main material, when the total weight of components 1 to 4 was 100% by weight, the ratio of component 4 (thermal conductive filler) was approximately 87% by weight, and in the case of a curing agent, the total weight of components 5 to 7 was 100 weight% %, the proportion of component 7 (thermal conductive filler) was approximately 87% by weight.

<Curable composition component>

<Presiding>

Component 1: First epoxy compound (Dimer acid modified epoxy resin, Kukdo Chemical, YD-171, epoxy equivalent (g/eq): 390 to 470, viscosity (cps at 25℃: 400 to 900)

Component 2: Multifunctional epoxy diluent (Kukdo Chemical, YH-300, trifunctional, epoxy equivalent (g/eq): 135 to 150, viscosity (cps at 25°C): 100 to 300)

Component 3: Second epoxy compound (bisphenol F-type epoxy compound, Kukdo Chemical Co., Ltd., YDF-175, epoxy equivalent (g/eq): 160 to 180, viscosity (cps at 25°C): 2,000 to 5,000)

Component 4: Thermally Conductive Filler (Alumina)

Blending ratio: 44:11:45 (component 1:component 2:component 3)

<curing agent>

Component 5: A mixture of styrenated phenol and aminoethyl piperazine (Kukdo Chemical, KH-1502, including 30 wt% of styrenated phenol)

Component 6: polyamide resin (amide-type amine) (Kukdo Chemical, G-930, A.H.E.W (g/eq): 120 to 140)

Component 7: Thermally Conductive Filler (Alumina)

Blending ratio: 70:30 (ingredient 5:component 6)

Examples 2 to 12

A two-component curable composition was prepared by mixing the main material and the curing agent in the same manner as in Example 1, except that the types and ratios of the components applied during the production of the main material and the curing agent were changed as shown in Table 1 below. In addition, although it is not described in Table 1, the thermally conductive filler was mix|blended with each of a main material and a hardening|curing agent similarly to Example 1. In addition, the number shown in Table 1 below is the weight ratio of each component.

Example One 2 3 4 5 6 7 8 9 10 11 12 residence ingredient 1 YD-171 44 40 25 40 30 50 40 40 40 40 40 KR208 50 ingredient 2 YH-300 11 40 75 45 40 40 50 40 40 40 40 40 LD-223 15 ingredient 3 YDF-175 45 KR-628 20 30 10 20 20 20 20 20 hardener ingredient 5 KH-1502 70 70 70 70 70 70 70 70 70 60 KH-1503 70 KH-1502-2 70 ingredient 6 G-930 30 30 30 30 30 30 30 30 30 G-640 30 30 D-400 30 PE-1 10

Comparative Examples 1 to 7

A two-component curable composition was prepared by mixing the main material and the curing agent in the same manner as in Example 1, except that the types and ratios of the components applied during the production of the main material and the curing agent were changed as shown in Table 2 below. In addition, although it is not described in Table 2, the thermally conductive filler was mix|blended with each of a main material and a hardening|curing agent similarly to Example 1. In addition, the number shown in Table 2 below is the weight ratio of each component.

comparative example One 2 3 4 5 6 7 residence ingredient 1 YD-171 44 20 60 40 40 40 KR-207 50 ingredient 2 YH-300 - 40 40 50 40 40 40 ingredient 3 YDF-175 56 KR-628 40 20 20 20 hardener ingredient 5 KH-1502 70 70 70 70 KH-252 70 A-3229 70 KH-8108 70 ingredient 6 G-0930 30 30 30 30 30 30 30

Specific details of each component applied in Examples and Comparative Examples are as follows.

YD-171: Dimer acid modified epoxy resin (Kukdo Chemical, YD-171, Epoxy equivalent (g/eq): 390 to 470, Viscosity (cps at 25℃): 400 to 900)

KR-208: Rubber Modified epoxy resin (Kukdo Chemical, KR-208, epoxy equivalent (g/eq): 270 to 330, viscosity (cps at 25℃): 8,000 to 12,000)

KR-207: Rubber Modified epoxy resin (Kukdo Chemical, KR-207, epoxy equivalent (g/eq): 190, viscosity (cps at 25℃): 2,000 to 3,000)

KR-628: Rubber Modified epoxy resin (Kukdo Chemical, KR-628, epoxy equivalent (g/eq): 220 to 240, viscosity (cps at 25℃): 40,000 to 60,000)

YH-300: polyfunctional epoxy diluent (Kukdo Chemical, YH-300, trifunctional, epoxy equivalent (g/eq): 135 to 150, viscosity (cps at 25°C): 100 to 300)

LD-223: polyfunctional epoxy diluent (Kukdo Chemical, LD-223, bifunctional, viscosity (cps at 25℃): 65)

YDF-175: bisphenol F-type epoxy compound (Kukdo Chemical, YDF-175, epoxy equivalent (g/eq): 160 to 180, viscosity (cps at 25°C): 2,000 to 5,000)

KH-1502: A mixture of styrenated phenol and aminoethyl piperazine (Kukdo Chemical, KH-1502, including 30 wt% of styrenated phenol)

KH-1502-2: A mixture of styrenated phenol and aminoethyl piperazine (Kukdo Chemical, KH-1502-2, including 20 wt% of styrenated phenol)

KH-1503: A mixture of styrenated phenol and aminoethyl piperazine (Kukdo Chemical, KH-1503, including 30 wt% of styrenated phenol)

KH-252: Polyamine modified curing agent (benzyl alcohol 10%, phenol 30% included) (Kukdo Chemical, KH-252, viscosity (cps at 25℃): 50 to 800)

Aradur-3229: Epoxy curing agent (humtsman, solid phenol derivative)

KH-8108: cycloaliphatic amine (Kukdo Chemical, KH-8108)

G-930: polyamide resin (amide-type amine) (Kukdo Chemical, G-0930, A.H.E.W (g/eq): 120 to 140)

G-640: polyamide resin (amide-type amine) (Kukdo Chemical, G-640, A.H.E.W (g/eq): 100 to 120)

D-400: etheramine (huntsman, D-400)

PE-1: thiol compound (Showa Denko, Karenz PE-1)

Table 3 below shows the evaluation results of physical properties confirmed for the Examples and Comparative Examples.

Adhesion (gf/cm) Insulation (resistance, GΩ) hardenability thermal conductivity Example One 548 17 Pass Pass 2 726 10 Pass Pass 3 223 5 Pass Pass 4 628 One Pass Pass 5 559 7 Pass Pass 6 712 4 Pass Pass 7 731 5 Pass Pass 8 811 2 Pass Pass 9 728 2 Pass Pass 10 728 2 Pass Pass 11 435 3 Pass Pass 12 405 2 Pass Pass comparative example One NG 56 Pass Pass 2 NG 6 Pass Pass 3 640 3 NG NG 4 NG 41 Pass Pass 5 767 less than 1 Pass Pass 6 NG 2 Pass Pass 7 NG One Pass Pass

10: module case
10a: lower plate
10b: side wall
10c: top plate
10d: guiding part
20: battery cell
30: resin layer
50a: injection hole
50b: observation hall
40: insulating layer

Claims (20)

a main material comprising an epoxy compound having an epoxy equivalent of 200 g/eq or more and a polyfunctional epoxy diluent; and a curing agent comprising a mixture of a phenol compound and an amine compound,
A curable composition for forming a cured product exhibiting an adhesive force of 200 gf/cm or more to a PET film, a thermal conductivity of 3 W/mK or more, and a resistance value of 1 GΩ or more. The curable composition according to claim 1, which is room temperature curable. The curable composition according to claim 1, wherein the epoxy compound having an epoxy equivalent weight of 200 g/eq or more is a dimer acid-modified epoxy compound or a rubber-modified epoxy compound. The curable composition according to claim 1, comprising 200 g/eq or more of the epoxy compound in the epoxy compound in an amount within the range of more than 20 wt% to less than 60 wt%. The curable composition according to claim 1, wherein the polyfunctional epoxy diluent is an aliphatic hydrocarbon compound having 2 to 5 glycidyloxy groups. The curable composition according to claim 1, wherein the main material comprises 15 to 400 parts by weight of the polyfunctional epoxy diluent relative to 100 parts by weight of the epoxy compound having an epoxy equivalent of 200 g/eq or more. The curable composition according to claim 1, wherein the main material further comprises an aromatic epoxy compound or a rubber-modified epoxy compound. The curable composition according to claim 7, wherein the aromatic epoxy compound is a bisphenol A epoxy compound or a bisphenol F epoxy compound. The curable composition according to claim 7, wherein the main material contains an aromatic epoxy compound in a ratio of 250 parts by weight or less based on 100 parts by weight of the epoxy compound having an epoxy equivalent of 200 g/eq or more. The curable composition according to claim 1, wherein the phenol compound is a styrenated phenol compound. The curable composition according to claim 1, wherein the amine compound is an ethylene amine compound. The curable composition according to claim 1, wherein the mixture comprises 15 to 60 parts by weight of the phenol compound based on 100 parts by weight of the amine compound. The curable composition according to claim 1, wherein the mixture of the phenol compound and the amine compound is included in the curing agent in a ratio of 10 to 100 wt%. The curable composition according to claim 1, wherein the mixture of the phenol compound and the amine compound is included in an amount of 10 to 300 parts by weight based on 100 parts by weight of the epoxy compound having an epoxy equivalent of 200 g/eq or more. The curable composition according to claim 1, wherein the curing agent further comprises an amide compound, an ether amine compound, or a thiol compound. The curable composition according to claim 1, wherein the main material or curing agent further comprises a thermally conductive filler. a module case having an upper plate, a lower plate, and a side wall, and having an internal space formed by the upper plate, the lower plate, and the side wall;
a plurality of battery cells existing in the inner space of the module case; and
A battery module comprising the curable composition of claim 1 and comprising a resin layer in contact with the plurality of battery cells and the lower plate or sidewall. The battery module according to claim 17, wherein the outer surface of the battery cell is a polyester layer. A battery pack comprising two or more battery modules of claim 17, which are electrically connected to each other. A vehicle comprising the battery pack of claim 19 .

Images