KR102458928B1 - Injection Device of Two-component Resin Composition - Google Patents

Abstract

The present application relates to a resin composition injection device for injecting a resin composition that can be applied to a battery module to improve heat dissipation performance. The injection device of the resin composition according to the present application can improve the overload applied to the injection device when the resin composition is injected into the battery module, and at the same time improve the filling and injection speed of the resin composition.

Description

Injection Device of Two-component Resin Composition

The present application relates to a device for injecting a two-component resin composition that is applied to a battery module and injects a two-component resin composition capable of improving heat dissipation performance.

Secondary batteries are being used as power sources for energy storage systems (ESS), electric vehicles (EVs) or hybrid vehicles (HEVs) as well as small high-tech electronic devices such as mobile phones, PDAs, and notebook computers.

When a large amount of power is required, such as driving a motor of an electric vehicle, a large-capacity modular 　 battery pack configured by connecting a battery module including a plurality of high-output battery cells is generally used.

The battery cell may mean a unit capable of functioning as a secondary battery. The battery module may mean that the plurality of electrically connected battery cells are accommodated in a module case. The battery pack may be manufactured by attaching a plurality of battery modules to a base material to be detachable and electrically connecting the plurality of battery modules.

In order to fix the battery cells accommodated in the module case, the resin composition may be injected into the module case provided with the battery cells. The resin composition may be a heat-dissipating adhesive resin composition including a large amount of thermally conductive fillers in order to fix the battery cells in the module case and to discharge heat generated from the battery cells to the outside. Patent Document 1 discloses a two-component resin composition applied to a battery module.

However, if the resin composition containing the high content filler stays in the injection device for a long time before injection into the battery module, the curing of the two-component resin composition proceeds to increase the viscosity, and thus there is a problem that the injection equipment is overloaded. there was.

Accordingly, there is a demand for an injection device for a two-part resin composition that can prevent an overload of the injection equipment from occurring by maintaining a low viscosity even when the time for which the two-part resin composition stays in the injection device is long.

Korean Patent Publication No. 2016-0105354

An object of the present application is to provide an injection device for a two-part resin composition that can prevent an overload of the injection equipment when injected into a battery module by maintaining a low viscosity even if the time the two-part resin composition stays in the injection device is long will do

Among the physical properties mentioned in this specification, when the measured temperature affects the result, unless otherwise specified, the corresponding physical property is a physical property measured at room temperature. The term ambient temperature is the natural temperature, either warmed or not desensitized, usually at any temperature in the range of about 10°C to 30°C, or on the order of about 23°C or about 25°C. In addition, unless otherwise stated in this specification, the unit of temperature is °C.

Among the physical properties mentioned in this specification, when the measured pressure affects the result, unless otherwise specified, the corresponding physical property is a physical property measured at normal pressure. The term atmospheric pressure is a natural pressure that has not been pressurized or depressurized, and usually about 1 atmosphere is referred to as atmospheric pressure.

In an example related to the present application, the present application relates to a device for injecting a two-component resin composition for injecting a two-part resin composition that is injected into a battery module and cured in the battery module to form a cured product.

1 is a view showing an injection device of an exemplary two-part resin composition of the present application. The two-component resin composition injection device (1) is a two-component resin composition injection unit (10); and a temperature control unit 20 disposed on the injection unit to control the temperature of the injection unit; and a control unit 30 for controlling the temperature control unit.

The arrangement of the temperature control unit on the injection unit is not particularly limited as long as the temperature control unit has a structure capable of adjusting the temperature of the injection unit. For example, the temperature control unit may be disposed to surround the entire injection unit, or may be disposed to surround a portion of the injection unit. Alternatively, it may be disposed attached to all or part of the injection unit, or may be disposed spaced apart from the injection unit.

The temperature control unit may include a heating means or a cooling means. The heating means or cooling means is not particularly limited, and a known heater or cooler may be used. By heating or cooling the injection unit by the heating means or cooling means of the temperature control unit, the temperature of the injection unit, specifically, the temperature of the two-component resin composition included in the injection unit can be adjusted to a desired temperature.

On the other hand, the control of the temperature by the heating means or the cooling means may be by a method of direct delivery or indirect delivery to the injection unit.

The direct transfer method means, for example, a method in which the temperature control unit directly contacts the injection unit to transfer heat or receive heat. As an example, there may be a method in which heat generated by the temperature control unit is transferred to the injection unit by conduction.

In addition, the indirect transmission method means, for example, a method in which the temperature control unit is positioned to be spaced apart from the injection unit to transmit heat or receive heat. As an example, there may be a method in which heat generated by the temperature control unit is transferred to the injection unit by convection. In another embodiment, there may be a method in which heat generated by the temperature control unit is transferred to the injection unit by radiation.

The temperature control unit may further include a temperature measuring means (not shown). The temperature measuring means is not particularly limited as long as it can measure the temperature of the injection part, specifically, the temperature of the two-component resin composition inside the mixer, and any known temperature measuring means can be used.

As an example, the injection device 1 of the two-component resin composition according to the present application may adjust the temperature of the injection unit 10 to be within the range of 5°C to 25°C. Temperature control of the injection unit may be performed by the control unit 30 . Specifically, when the temperature of the injection unit measured by the temperature measuring device of the temperature control unit 20 exceeds or falls short of the desired temperature range, the control unit 30 increases or decreases the temperature by the heating means or cooling means of the temperature control unit to increase or decrease the temperature of the resin composition The temperature can be adjusted to the desired temperature.

When the temperature of the injection part is less than 5 ° C, it takes a long time to raise the resin composition to the process temperature, and also the time it takes for the resin composition to become twice the viscosity (V ₂ ) compared to the initial viscosity (V ₁ ) (Vt ₂ ) Also exceeding the desired time, the time required to manufacture one battery module, that is, the process tact time may be increased. Therefore, module productivity may decrease. On the other hand, when the temperature of the injection part exceeds 25 ℃, the time (Vt ₂ ) until it becomes twice the viscosity (V ₂ ) compared to the initial viscosity (V ₁ ) may be shorter than the desired time, which is a resin composition This means that the rate of increase in viscosity of

When the temperature of the injection part satisfies within the range of 5°C to 25°C, that is, when the two-component resin composition in the injection part satisfies the range of 5°C to 25°C, the two-component resin composition is It may be possible to maintain a low viscosity for a time (Vt ₂ ) required until the initial viscosity (V ₁ ) is twice the viscosity (V ₂ ).

As an example, the temperature control unit may further include a moving means. By including the moving means in the temperature control unit, it is possible to easily adjust the arrangement of the temperature control unit on the injection unit. As an example, when the injection device for the two-component resin composition is not operated, the temperature control unit disposed on the injection unit may be separated from the injection unit, and separation of the temperature control unit may be facilitated by a moving means.

As an example, the injection unit includes a plurality of cartridges for accommodating the two-component resin composition, a mixer for receiving, mixing, and discharging the resin composition discharged from the plurality of cartridges, and a connector for fluidly connecting the plurality of cartridges and the mixer. may include 2 is a schematic diagram showing an exemplary injection unit 10 that can be applied to the injection device of the two-component resin composition of the present application.

As an example, the plurality of cartridges 11a and 11b for accommodating the two-component resin composition is not particularly limited, and a known cartridge may be used as long as it can accommodate the two-component resin composition. In one embodiment, the diameter of the cartridges 11a and 11b for accommodating the resin composition is about 15 mm to about 20 mm in a circular shape, and the diameter of the first discharge part for discharging the resin composition to the mixer through the connector is about 2 mm to about 5 mm. It has a circular shape, and the height is about 80 mm to 300 mm, and the total capacity may be 10 ml to 100 ml.

As an example, the cartridge 11 may have a pressing means (not shown). The pressing means is not particularly limited, and a known pressing means may be used. For example, the pressing means may use a texture ananlyser (TA). The pressurizing means may pressurize the cartridge to discharge the resin composition inside the cartridge to the mixer through the connecting pipe.

As an example, the mixer 13 for receiving and mixing the resin composition discharged from a plurality of cartridges is not particularly limited, and a known mixer may be used. In one embodiment, the mixer may be a static mixer. In one embodiment, the static mixer 13 connects the connector 12 from the two cartridges 11a and 11b to the two receiving parts 13a for accommodating the resin composition and the static mixer 13. has one discharge part 13b for discharging the two-component resin composition mixed by the It has a circular shape of 3 mm, and the number of elements in the static mixer may be about 5 to about 20. Meanwhile, the capacity of the mixer 13 may have a capacity satisfying the range of Formula 1 below.

[General formula 1]

V < Vt ₂ /td * Q

In Formula 1, V is the capacity of the static mixer, Vt ₂ is the time for which the viscosity of the resin composition is doubled, and a detailed description thereof will be given later. Meanwhile, in Formula 1, td is a dispensing process time, and Q is an injection amount per process unit time. When the capacity of the static mixer is large compared to the time for which the viscosity is doubled (Vt ₂ ), the residence time increases in excess of the amount per unit process, and the viscosity increases, the process speed is slowed down, or in severe cases, the mixer is hardened is likely to be blocked.

As an example, a connector for fluidly connecting the plurality of cartridges and the mixer is not particularly limited and a known connector may be used.

On the other hand, the above-described temperature control unit may be disposed in the cartridge, mixer and / or the connection pipe of the injection unit. For example, the temperature control unit may be disposed in the mixer of the injection unit. When the temperature control unit is disposed in the mixer of the injection unit to adjust the temperature of the two-component resin composition to be within the range of 5° C. to 25° C., it may be more advantageous to prevent overload of the injection equipment from occurring.

As an example, the two-part resin composition may include a main resin composition including a filler and a main resin; and a curing agent composition including a filler and a curing agent.

As an example, the main resin included in the main resin composition may mean a mixture of at least one of a silicone resin, an acrylic resin, a polyol resin, and an epoxy resin. Meanwhile, as the curing agent included in the curing agent composition, a known curing agent suitable for the main resin may be used. For example, when the main resin is a silicone resin, the curing agent can use a siloxane compound, when the main resin is a polyol resin, the curing agent can use an isocyanate compound, when the main resin is an epoxy resin, the curing agent can use an amine compound. In the case where the main resin is an acrylic resin, an isocyanate compound may be used as the curing agent.

As an example, the two-component resin composition according to the present application may be a polyol resin as the main resin, and the curing agent may be an isocyanate compound.

The polyol may be amorphous or may be an ester polyol having sufficiently low crystallinity. In the present specification, "amorphous" means a case in which the crystallization temperature (Tc) and the melting temperature (Tm) are not observed in a differential scanning calorimetry (DSC) analysis to be described later. At this time, the DSC analysis can be performed within the range of -80 to 60 °C at a rate of 10 °C / min, for example, after raising the temperature from 25 °C to 60 °C at the above rate, the temperature is reduced to -80 °C again, It can be made in a way that the temperature is raised to 60 ℃ again. In addition, in the above, "sufficiently low crystallinity" means that the melting point (Tm) observed in the DSC analysis is less than 15°C, about 10°C or less, 5°C or less, 0°C or less, -5°C or less, -10 It means a case of about ℃ or less or about -20℃ or less. In this case, the lower limit of the melting point is not particularly limited, but, for example, the melting point may be about -80°C or more, -75°C or more, or about -70°C or more. When the polyol is crystalline or does not satisfy the above melting point range, when crystallinity is strong (at room temperature), the difference in viscosity according to temperature tends to be large, so in the process of mixing the filler and the resin, the dispersion degree of the filler and the viscosity of the final mixture may have a detrimental effect on In addition, it may become difficult to satisfy physical properties such as cold resistance, heat resistance, and water resistance required for a two-component resin composition for a battery module.

In one example, as the polyol, for example, a carboxylic acid polyol or a caprolactone polyol may be used.

The carboxylic acid polyol may be formed by reacting a component including a carboxylic acid and a polyol (eg, a diol or a triol), and the caprolactone polyol includes caprolactone and a polyol (eg, a diol or a triol). It can be formed by reacting the components. In this case, the carboxylic acid may be a dicarboxylic acid.

In one example, the polyol may be a polyol represented by the following Chemical Formula 1 or 2.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, X is a unit derived from a carboxylic acid, and Y is a unit derived from a polyol. The unit derived from the polyol may be, for example, a triol unit or a diol unit. In addition, n and m may be any number, for example, n is a number within the range of 2 to 10, m is a number within the range of 1 to 10, A ₁ and A ₂ Each independently has 1 to 14 carbon atoms alkylene within the range of

As used herein, the term “carboxylic acid-derived unit” may refer to a portion excluding a carboxyl group in a carboxylic acid compound. Similarly, as used herein, the term “polyol-derived unit” may refer to a portion of a polyol compound structure excluding a hydroxyl group.

That is, when the hydroxyl group of the polyol and the carboxyl group of the carboxylic acid react, water (H ₂ O) molecules are desorbed by the condensation reaction to form an ester bond. As such, when the carboxylic acid forms an ester bond by the condensation reaction, the carboxylic acid-derived unit may mean a portion of the carboxylic acid structure that does not participate in the condensation reaction. In addition, the polyol-derived unit may refer to a portion of the polyol structure that does not participate in the condensation reaction.

In addition, Y in Formula 2 also represents a portion excluding the ester bond after the polyol forms an ester bond with caprolactone. That is, in Formula 2, the polyol-derived unit, Y, may mean a portion of the polyol structure that does not participate in the ester bond when the polyol and caprolactone form an ester bond. The ester bonds are shown in Formulas 1 and 2, respectively.

On the other hand, when the polyol-derived unit of Y in the formula is a unit derived from a polyol including three or more hydroxyl groups, such as a triol unit, a branched structure may be implemented in the Y portion in the formula structure.

In Formula 1, the type of the carboxylic acid-derived unit of X is not particularly limited, but in order to secure desired physical properties, a fatty acid compound, an aromatic compound having two or more carboxyl groups, an alicyclic compound having two or more carboxyl groups, and 2 It may be a unit derived from at least one compound selected from the group consisting of aliphatic compounds having at least two carboxyl groups.

The aromatic compound having two or more carboxyl groups may be, for example, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or tetrachlorophthalic acid.

The alicyclic compound having two or more carboxyl groups may be, for example, tetrahydrophthalic acid or hexahydrophthalic acid or tetrachlorophthalic acid.

In addition, the aliphatic compound having two or more carboxyl groups is, for example, oxalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, malic acid, glutaric acid, malonic acid, pimelic acid, suberic acid, 2,2-dimethyl succinic acid, 3,3-dimethylglutaric acid, 2,2-dimethylglutaric acid, maleic acid, fumaric acid or itaconic acid. In consideration of the low glass transition temperature, an aliphatic carboxylic acid-derived unit may be preferred over an aromatic carboxylic acid-derived unit.

Meanwhile, in Formulas 1 and 2, the type of the polyol-derived unit of Y is not particularly limited, but in order to secure desired physical properties, from the group consisting of an alicyclic compound having two or more hydroxyl groups and an aliphatic compound having two or more hydroxyl groups may be derived from one or more selected compounds.

The alicyclic compound having two or more hydroxyl groups may be, for example, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol.

In addition, the aliphatic compound having two or more hydroxyl groups is, for example, ethylene glycol, propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,2-ethylhexyldiol, 1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol, glycerin or trimethylol It may be propane.

Meanwhile, in Formula 1, n is an arbitrary number, and the range may be selected in consideration of the desired physical properties of the two-component resin composition or the cured resin layer thereof. For example, n can be about 2 to 10 or 2 to 5.

In addition, in Formula 2, m is an arbitrary number, and the range may be selected in consideration of the desired physical properties of the two-component resin composition or a resin layer that is a cured product thereof. For example, m is about 1 to 10 or 1 to It can be 5.

When n and m in Chemical Formulas 1 and 2 are out of the above ranges, the crystallinity of the polyol may be strengthened and the injection processability of the composition may be adversely affected.

In Formula 2, A ₁ and A ₂ are each independently alkylene having 1 to 14 carbon atoms. The number of carbon atoms may be selected in consideration of physical properties such as the desired insulating performance of the two-component resin composition or the cured resin layer thereof.

The molecular weight of the polyol may be adjusted in consideration of insulation performance, viscosity, durability, or adhesion, for example, in the range of about 300 to about 2,000. Unless otherwise specified, in the present specification, "molecular weight" may be a weight average molecular weight (Mw) measured using Gel Permeation Chromatograph (GPC). If out of the above range, the reliability of the resin layer after curing may be poor or problems related to volatile components may occur.

The type of isocyanate included in the curing agent is not particularly limited, but a non-aromatic isocyanate compound not containing an aromatic group may be used in consideration of the load value or viscosity of the mixed composition to be described later. When an aromatic isocyanate is used, it may be difficult to satisfy the load value and viscosity of the mixed resin composition, which will be described later, because the reaction rate is too fast and the glass transition temperature may be high.

Examples of the non-aromatic isocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate or tetramethylene diisocyanate. ; alicyclic polyisocyanates such as transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane diisocyanate or dicyclohexylmethane diisocyanate; Or any one or more of the above-mentioned carbodiimide-modified polyisocyanate or isocyanurate-modified polyisocyanate; etc. may be used. Also, mixtures of two or more of the compounds listed above may be used.

As another example, the two-component resin composition according to the present application includes an epoxy resin such as bisphenol A-type or bisphenol F-type liquid epoxy, rubber-modified epoxy or dimer acid-modified epoxy as the main resin, and a curing agent aliphatic amines such as ethylenediamine, diethylenetriamie, triethylenetetramine, tetraethylenepentamine or ethyleneamine, which can be cured at room temperature with low viscosity; or an alicyclic amine such as aminoethylpiperazine or aminoethylethanolamine.

As an example, the two-part resin composition may include a filler in each of the main resin composition and the curing agent composition. The filler may be a thermally conductive inorganic filler. In the present application, the term thermally conductive filler refers to a material having a thermal conductivity of about 1 W/mK or more, about 5 W/mK or more, about 10 W/mK or more, or about 15 W/mK or more. The thermal conductivity of the thermally conductive filler may be about 400 W/mK or less, about 350 W/mK or less, or about 300 W/mK or less. The type of thermally conductive filler that can be used is not particularly limited, and for example, aluminum oxide (alumina: Al ₂ O ₃ ), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si ₃ N ₄ ), carbide Ceramic particles such as silicon (SiC) beryllium oxide (BeO), zinc oxide (ZnO), magnesium oxide (MgO), or boehmite may be used.

In addition to the above fillers, various types of fillers may be used. For example, in order to secure the insulating properties of the resin layer in which the resin composition is cured, the use of a carbon filler such as graphite may be considered. Or, for example, a filler such as fumed silica, clay, aluminum hydroxide (Al(OH) ₃ ), magnesium hydroxide (Mg(OH) ₂ ) or calcium carbonate (CaCO ₃ ) may be used.

The shape or ratio of the filler is not particularly limited, and the viscosity of the resin composition, the curing rate of the mixed resin composition mixed by the mixer, the possibility of sedimentation of the mixed resin composition in the cured resin layer, the desired heat resistance or heat conduction Degree, insulation performance, charging effect, dispersibility or storage stability, etc. may be appropriately adjusted in consideration. In general, the larger the size of the filler, the higher the viscosity of the resin composition including the filler, the higher the possibility that the filler settles in the resin layer to be described later. Also, the smaller the size, the higher the thermal resistance tends to be. Therefore, in consideration of the above points, a filler of an appropriate type and size may be selected, and if necessary, two or more types of fillers may be used together. In addition, it is advantageous to use a spherical filler in consideration of the amount to be filled, but a filler in the form of a needle or plate may also be used in consideration of network formation or conductivity.

In one example, the two-component resin composition may use fillers having different average particle diameters. In the present application, the average particle size is the particle diameter (direct median) at 50% cumulative by volume of the particle size distribution, and the point at which the cumulative value becomes 50% on the cumulative curve with the total volume as 100% after obtaining the particle size distribution based on the volume. is the particle diameter of The average particle diameter (or D50) as described above may be measured by a laser diffraction method. Accordingly, the different average particle diameter may mean inorganic fillers having different particle diameters at 50% of the volume-based cumulative particle size distribution. In one embodiment, the filler of the present application may use an inorganic filler having at least three different average particle diameters.

The average particle diameter of the inorganic filler may be in the range of about 0.001 μm to about 100 μm. The average particle diameter of the filler may be about 0.01 μm or more, 0.1 μm or more, 0.5 μm or more, 1 μm or more, 2 μm or more, 3 μm or more, 4 μm or more, 5 μm or more, or about 6 μm or more in another example, 95 μm or less, 90 μm or less, 85 μm or less, 80 μm or less, 75 μm or less, 70 μm or less, 65 μm or less, 60 μm or less, 55 μm or less, 50 μm or less, 45 μm or less, 40 μm or less, 35 μm or less or less, 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, or about 10 μm or less.

On the other hand, when using inorganic fillers having at least three different average particle diameters, inorganic fillers having three different average particle diameters among the inorganic fillers within the range of the average particle diameter, that is, from about 0.001 μm to about 100 μm, are used for the physical properties of the resin composition, etc. It can be appropriately selected and used taking into account.

In order to obtain excellent heat dissipation performance, it may be considered that a high content of the thermally conductive filler is used. For example, it may be included in a ratio of about 70 parts by weight to 95 parts by weight based on 100 parts by weight of the resin composition. As another example, the resin composition may be included in an amount of about 75 parts by weight or more or about 80 parts by weight or more based on 100 parts by weight of the resin composition, and may be included in a ratio of about 90 parts by weight or less.

If the content of the filler exceeds about 95 parts by weight relative to 100 parts by weight of the resin composition, it is disadvantageous to satisfy the load value to be described later, and storage stability may deteriorate. On the other hand, if the content of the filler is less than about 70 parts by weight relative to 100 parts by weight of the resin composition, the battery module to which the resin composition is applied may have a disadvantage in securing heat dissipation performance due to low thermal conductivity.

Since the filler is included in the resin composition in a ratio within the above range, overload occurrence of injection equipment can be improved and storage stability can be improved, and the cured product of the resin composition has high thermal conductivity, so the cured product of the resin composition is applied to the battery module is advantageous in securing excellent heat dissipation performance. In addition, the higher the content of the filler within the above range, the higher the insulating performance may be.

In one example, the filler of the present application may have a moisture content of about 1,000 ppm or less. The moisture content can be measured with a Karl Fischer titrator (KR831) under the conditions of 10% relative humidity and 5.0 or less drift. In this case, the moisture content may be an average moisture content with respect to all fillers used in the resin composition. In the present application, a filler satisfying the above conditions may be selectively used, or after the filler to be used is dried in an oven at a temperature of about 200° C., the moisture content of the filler may be adjusted to satisfy the moisture content range. In another example, the upper limit of the moisture content of the filler may be about 800 ppm or less, 600 ppm or less, or about 400 ppm or less, and the lower limit thereof may be about 100 ppm or more or about 200 ppm or more.

As an example, the two-part resin composition may further include a reaction inhibitor. Specifically, the reaction inhibitor may be included in the main resin composition of the two-part resin composition. By including the reaction inhibitor in the main part, it is more advantageous to keep the viscosity low for a certain period of time even if the time that the two-part resin composition stays in the injection equipment is long.

The reaction inhibitor is not particularly limited as long as it can delay curing by reaction of the main resin and the curing agent. As an example, when the main resin is a polyol resin and the curing agent is isocyanate, a compound having a thiol group, a phenyl group, or an amine group may be used as the reaction inhibitor.

The reaction inhibitor as described above may react with isocyanate before the polyol resin. Therefore, when the main part contains a reaction inhibitor, in the step of mixing the main part and the curing agent part and injecting the two-component resin composition into the battery module, the reaction inhibitor of the main part reacts with the isocyanate of the curing agent part first, and the polyol resin reacts with the isocyanate can be delayed for a certain amount of time. Accordingly, the low viscosity can be maintained for a certain period of time from mixing the main part and the curing agent to injection into the battery module, so that the injection processability of the injection step of the battery module can be improved. In addition, it is possible to extend the replacement cycle of the injection equipment due to the occurrence of overload.

As an example, the reaction inhibitor may be a compound represented by the following formula (3).

[Formula 3]

In Formula 3, R ₁ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms unsubstituted or substituted with a thiol group (-SH); an aromatic hydrocarbon group unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a thiol group (-SH); or -Si(R ₃ ) ₃ , wherein R ₃ each independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ₂ is a single bond; an alkylene group having 1 to 12 carbon atoms, which is unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a thiol group (-SH).

As another example, in Formula 3, R ₁ is an alkyl group having 1 to 4 carbon atoms or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; an aromatic hydrocarbon group unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; Or represents -Si(R ₃ ) ₃ , wherein R ₃ may each independently be an alkoxy group having 1 to 4 carbon atoms. Meanwhile, in Formula 3, R ₂ is a single bond; It may be an alkylene group having 1 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms.

Meanwhile, in Formula 3, the aromatic hydrocarbon group means an aryl group or a heteroaryl group. In one embodiment, the aryl group may be a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a phenylenyl group, a chrysenyl group, or a fluorenyl group, but is not limited thereto. In addition, the heteroaryl group is a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, acri Diyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxa A jolyl group, an oxadiazolyl group, a thiadiazolyl group, a dibenzofuranyl group, etc., but are not limited thereto. In Formula 1, a single bond is a form in which atomic groups on both sides are directly bonded without a separate atom as a medium. means the case.

When the compound represented by Formula 3 is used as a reaction inhibitor, the reactivity with isocyanate as a curing agent may be improved, and thus the reaction delay efficiency between the polyol and the isocyanate may be improved.

As an example, the reaction inhibitor may be included in an amount of 0.05 to 0.5 parts by weight based on 100 parts by weight of the two-part resin composition. As another example, the resin composition may contain about 0.06 parts by weight or more, 0.07 parts by weight or more, 0.08 parts by weight or more, 0.09 parts by weight or more, or about 0.1 parts by weight or more, and about 0.45 parts by weight or less, 0.40 parts by weight or more, based on 100 parts by weight of the total resin composition. parts by weight or less, 0.35 parts by weight or less, or about 0.30 parts by weight or less.

If the content of the reaction inhibitor is low, the reaction delay efficiency of the polyol and isocyanate may decrease, and if the content of the reaction inhibitor is high, the time required to manufacture one battery module, that is, the process tact time may increase. have.

When the reaction inhibitor is included in the main resin composition within the above range, the reaction delay efficiency between the polyol and the isocyanate can be further improved, and thus it can be easier to maintain a low viscosity even if the residence time in the injection device of the two-component resin composition is long. .

As an example, a Brookfield HB type viscometer is used within 100 seconds of the curing reaction of the main resin of the main resin composition and the curing agent of the curing agent composition in a state where the temperature control unit disposed on the injection unit is operated. The time taken until the measured initial viscosity (V ₁ ) becomes twice the viscosity (V ₂ ) (Vt ₂ ) may be in the range of 15 minutes to 65 minutes.

The initial viscosity (V ₁ ) and twice the viscosity (V ₂ ) are measured in a shear rate range of 0.01 to 10.0/s using a Brookfield HB type viscometer, 2.4 It is the viscosity measured at the point /s.

Within 100 seconds of the initial viscosity (V ₁ ) is a time point when about 90 seconds have elapsed from the start of the curing reaction of the main resin of the main resin composition and the curing agent of the curing agent composition in a state in which the temperature control unit disposed on the injection unit is operated, 92 It may mean a time when seconds have elapsed, when 94 seconds have elapsed, when 96 seconds have elapsed, when 98 seconds have elapsed, or when about 100 seconds have elapsed.

As another example, the time taken until the viscosity (V ₂ ) doubles compared to the initial viscosity (V ₁ ) (Vt ₂ ) is about 16 minutes or more, 17 minutes or more, 18 minutes or more, 19 minutes or more, or about 20 minutes. or more, and may be about 64 minutes or less, 63 minutes or less, 62 minutes or less, 61 minutes or less, or about 60 minutes or less.

When the time (Vt ₂ ) required for the initial viscosity (V ₁ ) to become twice the viscosity (V ₂ ) compared to the initial viscosity (V 1 ) is less than 15 minutes, it means that the curing speed of the two-component resin composition is fast, and as described above When the two-component resin composition having a viscosity is injected into the injection equipment, overload of the injection equipment may be induced. On the other hand, when the time required for the viscosity (V ₂ ) to be twice as high as the initial viscosity (V ₁ ) exceeds 65 minutes, it means that the curing rate of the _two -component resin composition is very slow, and , thus, the time required to manufacture one battery module, ie, process tact time, may increase, and thus module productivity may decrease.

When the time required for the viscosity (V ₂ ) to be doubled compared to the initial viscosity (V ₁ ) (Vt ₂ ) is 15 to 65 minutes, even when the two-component resin composition stays in the injection device for a long time It is advantageous to overload the injection equipment and prevent it from occurring.

As an example, the mixed resin composition may further include an additive in addition to the main resin, a curing agent, and a filler. Physical properties such as insulation performance, adhesive strength, or viscosity of the mixed resin composition may vary depending on the type, type, and content of the additive to be added. Therefore, the mixed resin composition can achieve the desired physical properties by selecting and using the appropriate type, type and content of additives.

For example, the mixed resin composition may further include a thixotropic agent, a diluent, a dispersant, a surface treatment agent, a coupling agent, a flame retardant, or a plasticizer.

The thixotropic agent may adjust the viscosity according to the shear force of the mixed resin composition so that the manufacturing process of the battery module can be effectively performed. As a thixotropic agent that can be used, fumed silica and the like can be exemplified.

Diluents or dispersants are generally used to lower the viscosity of the mixed resin 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 introduced into the resin layer, which is a cured product of the mixed resin composition, and various types known in the art may be used without limitation as long as it can exhibit the above-described action.

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

In addition, the mixed resin composition may further include a flame retardant or a flame retardant auxiliary agent. In this case, a known flame retardant may be used without any particular limitation, for example, a flame retardant in the form of a solid filler or a liquid flame retardant may be applied. Examples of the flame retardant include organic flame retardants such as melamine cyanurate and inorganic flame retardants such as magnesium hydroxide. When the amount of filler included in the mixed resin composition is large, a liquid type flame retardant material (TEP, Triethyl phosphate or TCPP, tris(1,3-chloro-2-propyl)phosphate, etc.) may be used. In addition, a silane coupling agent capable of acting as a flame retardant synergist may be added.

The plasticizer may be used to improve the flexibility and elasticity of the resin layer, which is a cured product of the mixed resin composition, and thus, various types of plasticizers known in the art may be used without limitation, as long as they can exhibit the above action.

As an example, in a state in which the temperature control unit disposed on the injection unit is operated, the load value measured when the main resin of the main resin composition and the curing agent of the curing agent composition 30 minutes have elapsed from the start of the curing reaction may be less than 40 kgf. have.

The mixed resin composition obtained by mixing the main resin composition and the curing agent composition may have a load value of less than 40 kgf measured within 1 minute after mixing. In another example, it may be less than about 39 kgf, less than 38 kgf, less than 37 kgf, less than 36 kgf, or less than about 35 kgf, and may be about 20 kgf or more, 21 kgf or more, 22 kgf or more, 23 kgf or more, 24 kgf or more, or about 25 kgf or more. kgf or more.

In the present application, the load value of the two-component resin composition may be measured using an injection device for the two-part resin composition including an injection unit configured as shown in FIG. 2 .

Specifically, the main resin composition and the curing agent composition are respectively injected into the cartridges 11a and 11b, and the cartridge is pressurized at a constant speed of about 0.1 mm/s with a pressing means, and the main resin composition and the curing agent composition are injected with the mixer 13, , the main resin of the main resin composition and the curing agent of the curing agent composition in the mixer start to measure the force applied to the pressing means from the time when the curing reaction is first discharged 30 minutes after the start of the curing reaction, the maximum value of the force is The maximum value was taken as the load value. On the other hand, when 30 minutes have elapsed from the start of the curing reaction of the main resin and the curing agent, the pressure is stopped when the main resin composition and the curing agent composition are injected into the mixer 13 to reach about 95% of the capacity (volume) of the mixer. and means a time point when 30 minutes of the stop time has elapsed. Therefore, at the time when the 30 minutes have elapsed, the force applied to the pressing means is measured from the time the two-component resin composition is first discharged through the discharge part 13b of the mixer by re-pressurizing it at a constant speed of 1 mm/s with the pressing means. , the maximum value at the point where the force becomes the maximum value was taken as the load value.

In the case of a two-component resin composition, when the load value measured at 30 minutes after the start of the curing reaction exceeds 40 kgf, an overload occurs in the injection equipment of the two-component resin composition, thereby shortening the life of the injection device or the productivity of the battery module. This can fall. In addition, it may be difficult for the two-part resin composition to maintain a low viscosity in the injection equipment for a desired period of time. On the other hand, when the load value is less than 20 kgf, there is a possibility that overflow occurs after charging the two-component resin composition in the battery module or the storage stability of the two-component resin composition is deteriorated.

The injection device of the two-component resin composition according to the present application can keep the viscosity low even if the time for the two-part resin composition to stay in the injection device is long, thus preventing the overload of the injection equipment from occurring.

1 is a schematic diagram schematically showing an injection device for an exemplary resin composition.
2 is a schematic diagram showing an exemplary injection unit that can be applied to the injection device of the two-component resin composition of the present application.

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.

The initial viscosity (V _One ) twice the viscosity (V ₂ ) to the time it takes (Vt ₂ )

After the two-component resin composition prepared in Examples and Comparative Examples starts the curing reaction, that is, the main resin of the main resin composition and the curing agent of the curing agent composition start the curing reaction, the Brookfield HB type viscometer is measured within 100 seconds. The time (Vt ₂ ) until the viscosity (V ₂ ) doubled compared to the initial viscosity (V ₁ ) measured using the was measured.

The initial viscosity (V ₁ ) and twice the viscosity (V ₂ ) are measured in a shear rate range of 0.01 to 10.0/s using a Brookfield HB type viscometer, 2.4 It was set as the viscosity measured at the point /s.

load value

In the present application, the load value of the two-component resin composition was measured using an injection device for the two-part resin composition including the injection unit configured as shown in FIGS. 1 and 2 .

Specifically, as the cartridges 11a and 11b (Sulzer, AB050-01-10-01) in the injection device of the two-component resin composition including the injection unit configured as shown in FIG. 2, the upper part is a circle with a diameter of 18 mm, and the lower part is A circular shape with a diameter of 3 mm, a cartridge (11a, 11b) having a height of 100 mm, and an internal volume of 25 ml was used. In addition, as the static mixer 13 (Sulzer, MBH-06-16T), a circular discharge part 13b having a diameter of 2 mm was used. The static mixer is a stepped type, and the number of elements is 16. As the pressurizing means, TA (Texture Analyser) was applied. Meanwhile, a temperature control unit is disposed in the static mixer of the injection unit to maintain the temperature of the two-component resin composition present in the static mixer at a constant temperature.

The main resin composition and the curing agent composition prepared in Examples or Comparative Examples are respectively injected into the cartridge, and the upper part of the cartridge is pressed with a TA (texture analyzer) equipment at a constant speed of about 0.1 mm/s, and the main resin composition and the curing agent are mixed with a mixer. The composition is injected, and the force applied to the pressing means is measured from when the main resin of the main resin composition and the curing agent of the curing agent composition are first discharged 30 minutes after the start of the curing reaction in the mixer, and the force The said maximum value was made into the said load value at the point used as this maximum value. On the other hand, when 30 minutes have elapsed from the start of the curing reaction of the main resin and the curing agent, the pressure is stopped when the main resin composition and the curing agent composition are injected into the mixer to reach about 95% of the capacity (volume) of the mixer, and It means the time point when 30 minutes have elapsed. Therefore, at the time when the 30 minutes have elapsed, the force applied to the pressing means is measured from the time the two-component resin composition is first discharged through the discharge part of the mixer by re-pressurizing it at a constant speed of 1 mm/s by the pressing means, and the force is The maximum value was taken as the load value at the point at which it became the maximum value. On the other hand, the temperature of the mixer was maintained at a specific temperature by a temperature control means.

Example 1

Main resin: a caprolactone polyol represented by the following formula (2), wherein the number of repeating units (m in formula 2) is at a level of about 1 to 3, R ₁ and R ₂ are each alkylene having 4 carbon atoms, and a polyol As the derived unit (Y in Formula 3), a polyol including a 1,4-butanediol unit was used as the main resin.

[Formula 2]

Hardener: HDI (Hexamethylene diisocyanate) uretdione was used.

Filler: A first alumina filler having an average particle diameter of about 70 μm, a second alumina filler having an average particle diameter of about 20 μm, and a third alumina filler having an average particle diameter of about 2 μm were used. About 89 parts by weight of the filler based on 100 parts by weight of the two-part resin composition was divided and blended in equal amounts with the main resin and the curing agent.

Main resin composition: The main resin and filler were prepared by mixing with a planetary mixer.

Curing agent composition: The curing agent and the inorganic filler were prepared by mixing with a planetary mixer.

Two-component resin composition: A resin composition comprising the prepared main resin composition and curing agent composition as shown in FIGS. 1 and 2 so that the volume ratio of the main resin included in the main resin composition and the curing agent included in the curing agent composition is 1:1. It was prepared using an injection device. At this time, the temperature of the two-component resin composition in the mixer was maintained at about 25°C by using a temperature control unit.

Example 2

Main resin, curing agent and filler: The same main resin, curing agent and filler as in Example 1 were used.

Main resin composition and curing agent composition: A main resin composition and curing agent composition were prepared in the same manner as in Example 1.

Two-component resin composition: A two-part resin composition was prepared in the same manner as in Example 1, except that the temperature of the two-part resin composition in the mixer was maintained at about 15° C. using a temperature control unit.

Example 3

Main resin, curing agent and filler: The same main resin, curing agent and filler as in Example 1 were used.

Main resin composition and curing agent composition: A main resin composition and curing agent composition were prepared in the same manner as in Example 1.

Two-component resin composition: A two-part resin composition was prepared in the same manner as in Example 1, except that the temperature of the two-part resin composition in the mixer was maintained at about 5°C using a temperature control unit.

Comparative Example 1

Main resin, curing agent and filler: The same main resin, curing agent and filler as in Example 1 were used.

Main resin composition and curing agent composition: A main resin composition and curing agent composition were prepared in the same manner as in Example 1.

Two-component resin composition: A two-part resin composition was prepared in the same manner as in Example 1, except that the temperature of the two-part resin composition in the mixer was maintained at about 2°C using a temperature control unit.

Comparative Example 2

Main resin, curing agent and filler: The same main resin, curing agent and filler as in Example 1 were used.

Main resin composition and curing agent composition: A main resin composition and curing agent composition were prepared in the same manner as in Example 1.

Two-part resin composition: A two-part resin composition was prepared in the same manner as in Example 1, except that the temperature of the two-part resin composition in the mixer was maintained at about 30° C. using a temperature control unit.

division Vt ₂ (min) Load value (kgf) Example 1 about 37 minutes 36 Example 2 about 45 minutes 28 Example 3 about 60 minutes 25 Comparative Example 1 about 90 minutes 22 Comparative Example 2 about 14 minutes 42 Vt ₂ : The time it takes to reach twice the viscosity (V ₂ ) compared to the initial viscosity (V ₁ )

Through Table 1, when the temperature of the two-component resin composition in the injection unit is within the range of 5°C to 25°C, as in Examples 1 to 3, the initial viscosity (V ₁ ) compared to twice the viscosity (V ₂ ) until it becomes It can be seen that the required time (Vt ₂ ) is in the range of 15 minutes to 65 minutes, and the load value is less than 40 kgf.

In comparison, Comparative Example 1, in which the temperature of the two-component resin composition in the injection unit is 2°C, takes a long time to be stabilized by increasing the process temperature to 15°C to 30°C, and compared to the initial viscosity (V ₁ ) It can be seen that the time taken until the viscosity (V ₂ ) is doubled (Vt ₂ ) exceeds 90 minutes, so that the process tact time is decreased.

On the other hand, in Comparative Example 2, in which the temperature of the two-component resin composition in the injection part is 30 ° C, the load value of the injection equipment exceeds 40 kgf, and the injection equipment is overloaded, and it can be seen that the injection process into the battery module is deteriorated. .

1: Injection device of two-component resin composition
10: injection part of the two-component resin composition
11, 11a, 11b: cartridge
12, 12a, 12b: connector
13: mixer
13a: receptacle
13b: discharge unit
20: temperature control unit
30: control unit

Claims (9)

Injection part of the two-component resin composition; and a temperature control unit disposed on the injection unit to adjust the temperature of the injection unit. and a control unit for controlling the temperature control unit,
The temperature control unit adjusts the temperature of the injection unit to be within the range of 5°C to 25°C,
The two-part resin composition may include a main resin composition including a filler and a main resin; And a curing agent composition comprising a filler and a curing agent,
The main resin comprises a carboxylic acid polyol or caprolactone polyol, the curing agent comprises a non-aromatic isocyanate compound,
The filler is included in the range of 70 parts by weight to 95 parts by weight based on 100 parts by weight of the two-component resin composition,
Initial measurement using a Brookfield HB type viscometer within 100 seconds after the curing reaction of the main resin of the main resin composition and the curing agent of the curing agent composition in a state in which the temperature control unit disposed on the injection unit is operated The time taken until the _viscosity (V ₂ ) becomes twice the viscosity (V ₁ ) satisfies within the range of 15 minutes to 65 minutes,
Injection of a two-component resin composition having a load value of less than 40 kgf measured 30 minutes after the start of the curing reaction of the main resin of the main resin composition and the curing agent of the curing agent composition in a state in which the temperature control unit disposed on the injection unit is operated Device. The apparatus of claim 1, wherein the temperature control unit further comprises a moving means. The apparatus of claim 1, wherein the temperature control unit is separable from the injection unit. According to claim 1, wherein the injection unit is a plurality of cartridges for accommodating the two-component resin composition, a mixer for receiving, mixing, and discharging the resin composition discharged from the plurality of cartridges, and a connector for fluidly connecting the plurality of cartridges and the mixer. An injection device of a two-part resin composition comprising a. delete delete According to claim 1, wherein the filler is fumed silica, clay, calcium carbonate (CaCO ₃ ), aluminum oxide (Al ₂ O ₃ ), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si ₃ N ₄ ), carbide Silicon (SiC), beryllium oxide (BeO), zinc oxide (ZnO), aluminum hydroxide (Al(OH) ₃ ), boehmite (Boehmite) or a carbon filler is a two-component resin composition injection device. delete The injection device of claim 1, wherein the main resin composition further comprises a reaction inhibitor in an amount of 0.05 to 0.5 parts by weight based on 100 parts by weight of the two-part resin composition.

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