This application claims the benefit of priority based on the Republic of Korea Patent Application No. 10-2019-0111238 and Patent Application No. 10-2019-0111239 filed on September 09, 2019, and all contents disclosed in the documents of the Korean patent application is incorporated as part of this specification.
[2]
This application relates to curable compositions, battery modules, battery packs and automobiles.
background
[3]
The curing rate and curing progress of the curable composition need to be adjusted according to the application purpose. For example, depending on the application, the curable composition may require a certain waiting time after the initiation of curing.
[4]
In the present specification, the term curing initiation time refers to a time point at which the curable composition is exposed to a state and environment in which curing can proceed, and the term waiting time refers to a time when the curing can proceed, but is exposed to a state and environment in which the curing can proceed, but the degree of curing The amount of time that is delayed to the intended level.
[5]
For example, patent document 1 discloses the content which forms the resin layer which contacts a battery cell and a module case using a curable composition. Among the methods of forming the resin layer of Patent Document 1, a method of injecting a mixture of a two-component curable composition into a battery module using injection equipment such as a nozzle and curing the mixture is included. When the two-component curable composition is mixed, since the main resin and the curing agent of the main resin are in physical contact, generally the mixing time is the curing start time, and when the curing reaction proceeds, the viscosity of the composition usually increases. In the method of forming the resin layer as in Patent Document 1, since the composition is injected with a tube-type injection equipment having a relatively small diameter such as a nozzle, when the viscosity of the composition increases, a load is applied to the injection equipment. Therefore, in this case, a waiting time is required so that the viscosity can be maintained at a low level at least until the composition is injected into the module.
[6]
In addition, depending on the manufacturing line of the battery module, when the entire process such as a purging process is performed before injection of the composition, the mixed state after the two-component composition is mixed is maintained in the equipment until the entire process is completed. Since it needs to be maintained at
[7]
However, it is not easy to delay curing while the curable composition is exposed to curing conditions.
[8]
In addition, in the manufacturing process of the battery module, a battery cell or module inspection process is performed, and in this process, the top and bottom of the battery module are inverted in some cases. Therefore, in the inspection step, the composition injected into the module does not flow down or deviate from the position even when the top and bottom of the battery module are reversed, and the viscosity is increased so that the composition once injected does not occur again to be discharged back to the injection port. should be
[9]
During the manufacturing process of the battery module, when the reverse discharge occurs, a process of removing the reversely discharged composition needs to be performed. In this case, if the curing of the composition does not proceed excessively or, conversely, excessively proceeds, it is difficult to remove the reversely discharged composition. Accordingly, there is also a need to control the curing rate so that a degree of curing at a level that is easy to remove can be secured at the time of removal of the composition back-discharged during the process of the module.
[10]
In order to secure a suitable degree of curing in the inspection process and/or the removal process of the reversely discharged composition as described above, and to more efficiently proceed with the battery module manufacturing process, it is advantageous that curing proceeds quickly after the waiting time has elapsed.
[11]
However, it is not easy to secure a certain level of waiting time by delaying curing after the curing start time of the curable composition. In addition, if the curable composition is formulated so that curing occurs slowly, even if a certain amount of waiting time can be secured, in this case, curing cannot be made to proceed quickly after the waiting time has elapsed.
[12]
In addition, the curable composition for forming the resin layer disclosed in Patent Document 1 is a high-filling system in which an excessive amount of filler is blended in order to ensure high thermal conductivity in the resin layer. In the case of a curable composition of a high-fill system, the amount of components (such as a main agent and a curing agent) that advance the curing reaction is relatively small, and the contact probability of the components is affected by the problematic filler. In this case, it is more difficult to control the curing rate, and it is difficult to secure the waiting time or to allow the curing to proceed rapidly after the waiting time.
[13]
Moreover, the curable composition for forming the resin layer disclosed in patent document 1 needs to be comprised so that it may have a relatively low viscosity for injection|pouring. In this case, it is not easy to control the contact probability of components (such as the subject and the curing agent) that proceed with the curing reaction. Even in this case, it is more difficult to control the curing rate, and it is difficult to secure the waiting time or to allow the curing to proceed rapidly after the waiting time.
[14]
(Patent Document 1) Korean Patent Publication No. 2016-0105354
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[15]
An object of the present application is to provide a curable composition. An object of the present application is to provide a curable composition that can secure a waiting time, can freely adjust the waiting time according to the use, and can control the curing speed after the waiting time has elapsed relatively quickly .
[16]
An object of the present application is to provide a curable composition capable of securing the above properties even when the curable composition is a composition having a relatively low viscosity and/or a composition including an excessive amount of filler.
[17]
Another object of the present application is to provide a battery module, a battery pack, and/or a vehicle including the curable composition or a cured product thereof.
means of solving the problem
[18]
Among the physical properties mentioned in this specification, when the measurement temperature affects the result, unless otherwise specified, the physical property is a physical property measured at room temperature. The term room temperature refers to the natural temperature, both heated and undesensitized, which is usually a temperature in the range of about 10°C to 30°C, or a temperature on the order of about 23°C or about 25°C. In addition, unless otherwise specified in the specification, the unit of temperature is °C.
[19]
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 and depressurized, and usually about 1 atmosphere is referred to as atmospheric pressure.
[20]
The viscosity referred to herein is, unless otherwise specified, using a Brookfield HB type viscometer, at a temperature of about 25 °C, at a torque of about 90% and a shear rate of about 100 rpm. Means the measurement result.
[21]
The hardness referred to in this specification, unless otherwise specified, is the shore A hardness measured using an ASKER (durometer hardness) according to ASTM D 2240 standard, and a film having a thickness of about 4 mm It is the hardness measured in the thickness direction for the specimen of the shape.
[22]
As used herein, the term curing initiation time refers to a time point at which the curable composition is exposed to an environment capable of curing. For example, in the case of a room temperature curable composition, the time when the composition is exposed to room temperature The curing initiation time is the time when a degree of heat is started to be applied, and in the case of a light-curable composition, the time when light to a degree capable of being cured is started to be applied to the composition. The two-component curable composition usually consists of a physically separated main composition and a curing agent composition, and curing does not proceed even when exposed to the above conditions before the main and curing agent compositions are mixed. Therefore, the curing start time of the two-component curable composition is the time when the main agent and the curing agent composition are mixed and exposed to the above conditions. For example, in the case of a room temperature curable two-component composition, if the main agent and the curing agent composition are mixed at room temperature, the mixing time is the curing start time, the mixing is performed at a temperature other than room temperature, and the mixture is exposed to room temperature after mixing , The room temperature exposure time is the curing start time.
[23]
As used herein, the term curing delay refers to a state in which the curing reaction does not occur or the degree of curing reaction is low to such an extent that the curable composition is exposed to an environment capable of curing, but the viscosity does not increase to an intended level.
[24]
In the present specification, the term waiting time is a time from the start of the curing to the end of the curing delay state.
[25]
This application relates to a curable composition. By using the curable composition of the present application, it is possible to secure a waiting time of the curable composition suitable for use, and after the waiting time is over, it is possible to induce fast curing at an intended level.
[26]
When the curable composition of the present application is used, for example, when injecting the curable composition using a tube-type device having a relatively small diameter such as a nozzle and/or when the injection is performed in a relatively narrow space It can also not put a load on the equipment. For example, in the manufacturing process of the battery module disclosed in Patent Document 1, if the injection of the curable composition into the module case is performed while the battery cells are mounted in the module case, the curable composition enters the narrow space inside the module case. will be injected In this case, a load may be applied to the equipment due to the generation of internal pressure, but when the curable composition of the present application is used, the load is not applied to the equipment or is minimized even in this case.
[27]
The curable composition of the present application may be suitably used for a variety of uses, and for example, may be suitably used for manufacturing a battery module or battery pack (in particular, manufacturing a battery module or pack disclosed in Patent Document 1). In this case, the curable composition of the present application may be injected into the case of the battery module and used to contact one or more battery cells present in the battery module to fix the battery cells in the battery module.
[28]
The curable composition of the present application may be a one-component composition or a two-component composition. Two-part compositions typically include a physically separate subject composition and a curing agent composition. Accordingly, the description of the curable composition in the present specification refers to the content of the one-component curable composition, the subject matter of the two-component curable composition or the content of the curing agent composition, or a mixture or reactant of the subject and the curing agent composition of the two-component curable composition. It may be about
[29]
The curable composition of the present application may be, for example, a urethane composition. The term urethane composition may refer to a composition that can be cured to form a polyurethane.
[30]
The curable composition of the present application may be of room temperature curing type, room temperature and humidity curing type, moisture curing type, heat curing type or light curing type. When the curable composition is applied to the manufacture of the battery module shown in Patent Document 1, the curable composition may be composed of a room temperature curable type.
[31]
The curable composition of the present application may include at least a polyol, a reaction inhibitor, a catalyst, and a filler.
[32]
The curable composition of the present application exhibits an appropriate waiting time after the start of curing. Therefore, for example, the curable composition takes the time required to become twice the viscosity compared to the initial viscosity (V t2 ) (that is, when the initial viscosity is V 1 , it takes to show a viscosity of 2V 1 from the start of curing time) may be 15 minutes or longer.
[33]
The term initial viscosity means the viscosity of the curable composition at the time of initiation of curing. In practice, since it may be technically difficult to measure the viscosity of the curable composition immediately at the onset of curing, the initial viscosity may be determined within about 3 minutes, within about 2.5 minutes, within about 1.5 minutes, or within about 1 minute from the onset of curing. The measured viscosity may also be defined as the initial viscosity, and the viscosity measured after about 10 seconds, about 20 seconds, or about 60 seconds from the start of curing may also be defined as the initial viscosity.
[34]
In general, the viscosity of the curable composition increases as the curing reaction proceeds, and the curable composition of the present application may exhibit a waiting time in which the required time (V t2 ) is 15 minutes or more. The required time V t2 may be controlled to a desired level as needed. For example, the required time V t2 is about 17 minutes or more, 19 minutes or more, 21 minutes or more, 23 minutes or more, 25 minutes or more, 27 minutes or more, 29 minutes or more, 31 minutes or more, 33 minutes or more, 35 minutes or more, 37 minutes or more, 39 minutes or more, 41 minutes or more, 43 minutes or more, 45 minutes or more, 47 minutes or more, 49 minutes or more, 51 minutes or more, 53 minutes or more, 55 minutes or more, 57 minutes or more, 59 minutes or more. or more, 61 minutes or more, 63 minutes or more, 65 minutes or more, or 67 minutes or more and/or 100 minutes or less, 98 minutes or less, 96 minutes or less, 94 minutes or less, 92 minutes or less, 90 minutes or less, 88 minutes or less, 86 minutes or less, 84 minutes or less, 82 minutes or less, 80 minutes or less, 78 minutes or less, 76 minutes or less, 74 minutes or less, 72 minutes or less, 70 minutes or less, 68 minutes or less, 66 minutes or less, 64 minutes or less, 62 minutes or less or less, 60 minutes or less, 58 minutes or less, 56 minutes or less, 54 minutes or less, 52 minutes or less, 50 minutes or less, 48 ​​minutes or less, 46 minutes or less, 44 minutes or less, 42 minutes or less, 40 minutes or less, 38 minutes or less, It may be further adjusted within the range of 36 minutes or less, 34 minutes or less, 32 minutes or less, 30 minutes or less, 28 minutes or less, 26 minutes or less, 24 minutes or less, 22 minutes or less, or 20 minutes or less.
[35]
For example, the curable composition having a time required (Vt 2 ) adjusted within the above range may be suitably applied to the manufacture of the battery module disclosed in Patent Document 1. The curable composition exhibiting such a waiting time may be applied to the manufacturing process to reduce the load applied to the equipment, and to secure suitable work fairness (eg, secure a suitable process tact time).
[36]
In another example, the curable composition may have a Shore A hardness confirmation time (Ht i ) in the range of 40 minutes to 300 minutes. The term Shore A hardness confirmation time (Ht i ) is the time taken from the start of the curing until the shore A hardness of the curable composition starts to be confirmed. As described above, in general, the curable composition starts to increase in viscosity after curing starts, and thus hardness also increases. However, since the hardness is very low in a state where the degree of curing is low, the hardness of the curable composition cannot be confirmed using equipment. Therefore, in order to measure the hardness of the curable composition, it is necessary to proceed with curing to a certain level or more after the curing start time. For example, the Shore A hardness confirmation time (Ht i ) of 40 minutes means that the curing start time This means that after 40 minutes, the hardness starts to be measured in the instrument. Accordingly, a long required time (Ht i ) may mean a long waiting time, and conversely, a short time may mean that the curing speed after the waiting time is fast.
[37]
The confirmation time (Ht i ) may also be adjusted to a desired level. For example, the required time (Ht i ) is about 41 minutes or more, 42 minutes or more, 43 minutes or more, 44 minutes or more, 45 minutes or more, 46 minutes or more, 47 minutes or more, 48 minutes or more, 49 minutes or more, 50 minutes or more, 55 minutes or more, 60 minutes or more, 65 minutes or more, 70 minutes or more, 75 minutes or more, 80 minutes or more, 85 minutes or more, 90 minutes or more, 95 minutes or more, 100 minutes or more, 110 minutes or more, 120 minutes or more. or more, 130 minutes or more, 140 minutes or more, 150 minutes or more, 160 minutes or more, 170 minutes or more, 180 minutes or more, 190 minutes or more, or 200 minutes or more and/or 200 minutes or less, 190 minutes or less, 180 minutes or less, 170 minutes or less, 160 minutes or less, 150 minutes or less, 140 minutes or less, 130 minutes or less, 120 minutes or less, 110 minutes or less, 100 minutes or less, 90 minutes or less, 80 minutes or less, 70 minutes or less, 60 minutes or less, or 50 minutes or less It may be further adjusted within the following range.
[38]
For example, the curable composition having the confirmation time (Ht i ) adjusted within the above range may be suitably applied to the manufacture of the battery module disclosed in Patent Document 1. Such a curable composition may be applied to the manufacturing process to reduce the load applied to the equipment, and secure suitable work fairness (eg, secure tact time for a suitable process).
[39]
In one example, the difference (H ti -V t2 ) between the required time (V t2 ) and the confirmation time (H ti ) in the curable composition may be in the range of 25 minutes to 300 minutes. The difference (H ti -V t2 ) may also be controlled to a desired level if necessary. For example, the difference (H ti -V t2) is about 27 minutes or more, 29 minutes or more, 31 minutes or more, 33 minutes or more, 35 minutes or more, 37 minutes or more, 39 minutes or more, 41 minutes or more, 43 minutes or more, 45 minutes or more, 47 minutes or more, 49 minutes. or more, 51 minutes or more, 53 minutes or more, 55 minutes or more, 57 minutes or more, 59 minutes or more, 61 minutes or more, 63 minutes or more, 65 minutes or more, 67 minutes or more, 70 minutes or more, 80 minutes or more, 90 minutes or more, 100 minutes or more, 110 minutes or more, 120 minutes or more, or 130 minutes or more and/or 250 minutes or less, 200 minutes or less, 150 minutes or less, 100 minutes or less, 98 minutes or less, 96 minutes or less, 94 minutes or less, 92 minutes or less, 90 minutes or less, 88 minutes or less, 86 minutes or less, 84 minutes or less, 82 minutes or less, 80 minutes or less, 78 minutes or less, 76 minutes or less, 74 minutes or less, 72 minutes or less, 70 minutes or less, 68 minutes or less, 66 minutes or less, 64 minutes or less, 62 minutes or less, 60 minutes or less, 58 minutes or less, 56 minutes or less, 54 minutes or less, 52 minutes or less, 50 minutes or less, 48 ​​minutes or less, 46 minutes or less, 44 minutes or less, 42 minutes or less or less, 40 minutes or less, 38 minutes or less, 36 minutes or less, 34 minutes or less, 32 minutes or less, or 30 minutes or less.
[40]
For example, the curable composition having a controlled difference (H ti -Vt 2 ) within the above range may be suitably applied to the manufacture of the battery module disclosed in Patent Document 1. Such a curable composition may be applied to the manufacturing process to reduce the load applied to the equipment, and secure suitable work fairness (eg, secure tact time for a suitable process).
[41]
In one example, the curable composition may have a shore A hardness 40 confirmation time (Ht 40 ) in the range of 40 minutes to 300 minutes. The term Shore A hardness 40 confirmation time (Ht 40 ) is the time taken from the start of the curing until the shore A hardness of the curable composition starts to be confirmed as 40. The required time (Ht 40 ) may also be adjusted to a desired level depending on the purpose. For example, the required time (Ht 40) is 290 minutes or less, 280 minutes or less, 270 minutes or less, 260 minutes or less, 250 minutes or less, 240 minutes or less, 230 minutes or less, 220 minutes or less, 210 minutes or less, 200 minutes or less, 190 minutes or less, 180 minutes or less , 170 minutes or less, 160 minutes or less, 150 minutes or less, 140 minutes or less, 130 minutes or less, 120 minutes or less, 118 minutes or less, 116 minutes or less, 114 minutes or less, 112 minutes or less, 100 minutes or less, 90 minutes or less, 80 minutes or less, 70 minutes or less, 60 minutes or less, or 50 minutes or less and/or about 45 minutes or more, about 50 minutes or more, 52 minutes or more, 54 minutes or more, 56 minutes or more, 58 minutes or more, about 60 minutes or more. , 70 minutes or more, 80 minutes or more, 90 minutes or more, 100 minutes or more, 110 minutes or more, 120 minutes or more, 130 minutes or more, 140 minutes or more, 150 minutes or more, 160 minutes or more, 170 minutes or more, 180 minutes or more, 190 Minutes or more, 200 minutes or more, 210 minutes or more, 220 minutes or more, 230 minutes or more, 240 minutes or more, 250 minutes or more, 260 minutes or more, 270 minutes or more, 280 minutes or more, or 290 minutes or more. have.
[42]
For example, the curable composition having a controlled confirmation time (H t40 ) within the above range may be suitably applied to the manufacture of the battery module disclosed in Patent Document 1. The curable composition exhibiting such a waiting time may be applied to the manufacturing process to reduce the load applied to the equipment, and to secure suitable work fairness (eg, secure a suitable process tact time).
[43]
In one example, the difference (H t40 -H ti ) between the confirmation times H ti and H t40 may be in the range of 1 minute to 30 minutes. The difference (H t40 -H ti ) may also be controlled to a desired level if necessary. For example, the difference (H t40 -H ti ) is within a range of about 2 minutes or more, 3 minutes or more, 4 minutes or more, or 4.5 minutes or more and/or 25 minutes or less, 20 minutes or less, 15 minutes or less, 10 minutes or more. or less, 9 minutes or less, 8 minutes or less, 7 minutes or less, 6 minutes or less, or 5.5 minutes or less.
[44]
The curable composition having a difference in the confirmation time (H t40 -H ti ) means that rapid curing occurs after a waiting time, and this curable composition may be suitably applied to, for example, the manufacture of a battery module disclosed in Patent Document 1 have. Such a curable composition may be applied to the manufacturing process to reduce the load applied to the equipment, and secure suitable work fairness (eg, secure tact time for a suitable process).
[45]
In one example, the curable composition may have a Shore A hardness 90 confirmation time (Ht 90 ) in the range of 70 minutes to 400 minutes. The term Shore A hardness 90 confirmation time (Ht 40 ) is the time taken from the start of the curing until the shore A hardness of the curable composition starts to be confirmed as 90. The required time (Ht 90 ) may also be adjusted to a desired level depending on the purpose. For example, the required time (Ht 90 ) is 75 minutes or more, 80 minutes or more, 82 minutes or more, 84 minutes or more, 86 minutes or more, 88 minutes or more, about 90 minutes or more, 100 minutes or more, 150 minutes or more, 200 minutes or more or 250 minutes or more and/or 350 minutes or less, 300 minutes or less, 250 minutes or less, 200 minutes or less, about 178 minutes or less, 176 minutes or less, 174 minutes or less, about 172 minutes or less, 165 minutes or less, 160 minutes or less, 155 minutes or less, 150 minutes or less, 145 minutes or less, 140 minutes or less, 135 minutes or less, 130 minutes or less, 125 minutes or less, 120 minutes or less, 115 minutes or less, 110 minutes or less, 105 minutes or less, 100 minutes or less It may be further adjusted within the range of less than or equal to 90 minutes or less than or equal to 80 minutes.
[46]
For example, the curable composition having a controlled confirmation time (H t90 ) within the above range may be suitably applied to the manufacture of the battery module disclosed in Patent Document 1. The curable composition exhibiting such a waiting time may be applied to the manufacturing process to reduce the load applied to the equipment, and to secure suitable work fairness (eg, secure a suitable process tact time).
[47]
In one example, the difference (H t90 -H t40 ) between the confirmation times H t90 and H t40 in the curable composition may be 200 minutes or less. The difference (H t90 -H t40 ) is 190 minutes or less, 180 minutes or less, 170 minutes or less, 160 minutes or less, 150 minutes or less, 140 minutes or less, 130 minutes or less, 120 minutes or less, 110 minutes or less, 100 minutes or less , 90 minutes or less, 80 minutes or less, 70 minutes or less, 68 minutes or less, 66 minutes or less, about 64 minutes or less, 60 minutes or less, 55 minutes or less, 50 minutes or less, or 45 minutes or less, or 40 minutes or less; and/ or 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, 30 minutes or more, 35 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, 55 minutes or more, 60 minutes or more, 65 minutes or more, 70 Minutes or more, 75 minutes or more, 80 minutes or more, 85 minutes or more, 90 minutes or more, 95 minutes or more, 100 minutes or more, 110 minutes or more, 120 minutes or more, 130 minutes or more, 140 minutes or more, 150 minutes or more, 160 minutes or more , may be further adjusted within the range of 170 minutes or more, 180 minutes or more, or 190 minutes or more.
[48]
A curable composition having a difference in the confirmation time (H t90 -H t40 ) means that rapid curing occurs after a waiting time, and this curable composition can be suitably applied to, for example, the manufacture of a battery module disclosed in Patent Document 1 have. Such a curable composition may be applied to the manufacturing process to reduce the load applied to the equipment, and secure suitable work fairness (eg, secure tact time for a suitable process).
[49]
In one example, the curable composition of the present application may have a low initial load value (Li). The term load value, assuming that the curable composition is injected by equipment such as a relatively narrow diameter tube such as a nozzle, quantifies the load applied to the equipment in the process, and is a value measured in a manner described below am. In addition, the term initial stage load value is the value which quantified the said load value of the curable composition at the time of hardening start. The unit of the load value is kgf.
[50]
In the curable composition of the present application, the initial load value (Li) may be in the range of 10 to 35 kgf. In another example, the initial load value Li is about 10 kgf or more, 11 kgf or more, 12 kgf or more, 13 kgf or more, 14 kgf or more, 15 kgf or more, 16 kgf or more, 17 kgf or more, 18 kgf or more, 19 kgf or more. or more, 20 kgf or more, 21 kgf or more, 22 kgf or more, 23 kgf or more, 24 kgf or more, 25 kgf or more, 26 kgf or more, 27 kgf or more, or 28 kgf or more and/or about 35 kgf or less, 34 kgf or less , 33 kgf or less, 32 kgf or less, 31 kgf or less, 30 kgf or less, 29 kgf or less, 28 kgf or less, 27 kgf or less, 26 kgf or less, 25 kgf or less, 24 kgf or less, 23 kgf or less, or 22 kgf or less may be further adjusted within
[51]
In the present application, the curable composition may also have a load value change rate of 1 to 2 according to Equation 1 below.
[52]
[Equation 1]
[53]
Load value change rate = Lf/Li
[54]
In Equation 1, Li is the initial load value, and Lf is the load value 30 minutes after the start of curing.
[55]
A large load value change rate means a short waiting time, and a low load value change rate means a long standby time.
[56]
In another example, the load value change rate (Lf/Li) may be about 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, or 1.1 or less.
[57]
Also, the load value Lf may be about 50 kgf or less. In another example, the load value Lf is about 20 kgf or more, 22 kgf or more, 24 kgf or more, 26 kgf or more, 28 kgf or more, 30 kgf or more, 32 kgf or more, 34 kgf or more, 36 kgf or more, 38 kgf or more. or more, 40 kgf or more, 42 kgf or more, or 44 kgf or more and/or about 48 kgf or less, 46 kgf or less, 44 kgf or less, 42 kgf or less, 40 kgf or less, 38 kgf or less, 36 kgf or less, 34 kgf or less , 32 kgf or less, 30 kgf or less, 28 kgf or less, or 26 kgf or less may be further controlled.
[58]
1 is a diagram schematically showing the configuration of an apparatus 1 for measuring the load value. The load value is as shown in FIG. 1, in the process of putting the curable composition into the cartridges (2, 2a, 2b), pressurizing it with the pressing means (3, 3a, 3b), and discharging it through the mixer, the pressing means (3, 3a) , can be defined as the maximum force applied to 3b).
[59]
For example, the load values ​​Li and Lf pressurize the curable composition in the cartridges 2, 2a, 2b at a constant velocity of about 1 mm/s with the pressurizing means 3a, 3b, and discharge it via the mixer 5 It is possible to start measuring the force applied to the pressing means from the time the force is applied, and the force at the time when the force becomes the maximum may be the load values ​​Li and Lf.
[60]
The device 1 of FIG. 1 is a device for measuring a load value for a two-component curable composition, and has a structure in which two cartridges 2a and 2b are mounted to respectively load the main composition and the curing agent composition, but the one-component curable composition When measuring the load value of the composition, only one cartridge may be mounted.
[61]
In addition, the load value Lf may be measured by confirming the maximum force in the same manner when 30 minutes have elapsed after the start of curing. For a two-component composition, for example, the main agent and the curing agent composition are injected into the two cartridges 2a and 2b, respectively, and pressurized at a constant speed of 1 mm/s with the pressurizing means 3a and 3b, and the main agent composition with the mixer 5 While injecting the composition and curing agent composition, when the amount of the injected composition reaches 95% of the capacity (volume) of the mixer, stop the pressurization, wait for about 30 minutes, and then pressurize again at the same constant velocity (1mm/s) Starting from, the maximum force applied to the pressing means may be measured as the load value Lf.
[62]
When the force applied to the pressing means is monitored in this way, the force usually increases with the lapse of time from the start of the pressing, and then starts to decrease again after a certain time has elapsed, or the increase stops, and the force is at a certain level. This shows a continuous trend. Accordingly, the maximum force may be a force just before the point in time when the decrease of the force starts, or may be a force maintained at the constant level.
[63]
The types of the cartridge 2, the mixer 5 and the pressurizing means 3 applied in the measuring device 1 are described in the embodiment section.
[64]
The curable composition of the present application, depending on the use, the above-described required time or confirmation time (V t2 , H ti , H t40 and H t90 ) and/or their difference (H ti -V t2 , H t40 -H ti and H ) t90 -H t40 ) may be composed to satisfy any one or two or more or all of them.
[65]
The times V t2 , H ti , H t40 and H t90 and their differences H ti -V t2 , H t40 -H ti and H t90 -H t40 are, for example, The amount of the reaction inhibitor and/or catalyst, the functional group of the reaction inhibitor, etc. can be controlled to control.
[66]
The polyol contained in the curable composition may be a main resin. When the curable composition is a urethane composition, the polyol (base resin) may react with a curing agent to form a polyurethane. In this case, an isocyanate compound may be used as the curing agent. The polyurethane may include both the polyol-derived unit and the isocyanate compound-derived unit. The polyol-derived unit may be a unit formed by the urethane reaction of the polyol with the isocyanate compound, and the isocyanate compound-derived unit may be a unit formed by the urethane reaction of the isocyanate compound with the polyol.
[67]
The ratio of the polyol in the curable composition may be adjusted within the range of about 0.5 to 40 parts by weight based on 100 parts by weight of the filler. When the curable composition is the main composition of the two-component curable composition, the ratio is the ratio of the weight of all the fillers and the weight of the polyol included in the main composition, and in the case of a mixture of the main composition of the two-component curable composition and the curing agent composition, The ratio is the ratio of the weight of all fillers contained in the mixture to the weight of the polyol. In another example, the ratio is about 1 part by weight or more, 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more, 4 parts by weight or more, 4.5 parts by weight or more, 5 parts by weight or more. or more, 5.5 parts by weight or more, 6 parts by weight or more, 6.5 parts by weight or more, 7 parts by weight or more, 7.5 parts by weight or more, 8 parts by weight or more, 8.5 parts by weight or more, or 9 parts by weight or more and/or 38 parts by weight or less. , 36 parts by weight or less, 34 parts by weight or less, 32 parts by weight or less, 30 parts by weight or less, 28 parts by weight or less, 26 parts by weight or less, 24 parts by weight or less, 22 parts by weight or less, 20 parts by weight or less, 18 parts by weight or less , 16 parts by weight or less, 14 parts by weight or less, 12 parts by weight or less, 10 parts by weight or less, 8 parts by weight or less, or 6 parts by weight or less. Such a ratio is a ratio that can appear in the case of a high-fill system in which the content of filler in the curable composition is excessive.
[68]
As the polyol, a known polyol may be applied without any particular limitation. For example, as the polyol, it is possible to apply a polyol which is applied to the formation of polyurethane. As such polyols, so-called polyether polyols, polyester polyols and/or other polyols (polycarbonate polyols, polybutadiene polyols, acrylic polyols, etc.) are known.
[69]
In one example, in consideration of the possibility of controlling an appropriate curing rate, a so-called aliphatic polyol may be used as the polyol.
[70]
As the polyol, a polyol having a hydroxyl value (Hydroxyl value or OH value) in the range of about 50 to 500 may be used. The unit of the hydroxyl value is mgKOH/g, and is a value measured according to a standard test method (ASTM E 1899-08). In another example, the hydroxyl value is about 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, 110 or more, 120 or more, 130 or more, 140 or more, 150 or more, 160 or more, 170 or more, 180 or more, 190 or more, 200 or more, 210 or more, 220 or more, 230 or more, 240 or more, 250 or more, 260 or more, or 270 or more and/or 490 or less, 480 or less, 470 or less, 460 or less, 450 or less, 440 or less, 430 or less, 420 or less It may be further adjusted within the range of 410 or less, 400 or less, 390 or less, 380 or less, 370 or less, 360 or less, 350 or less, 340 or less, 330 or less, 320 or less, 310 or less, or 300 or less.
[71]
As the polyol, a polyol having a molecular weight in the range of about 100 to 3000 may be used in consideration of an appropriate curing rate, viscosity, durability, and/or adhesion. Unless otherwise specified, in the present specification, the term molecular weight is a weight average molecular weight (Mw) measured using Gel Permeation Chromatograph (GPC), and the unit is g/mol. The molecular weight is in another example 150 or more, 200 or more, 250 or more, 300 or more, or 350 or more and/or 2500 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 700 or less, 600 or less, or 500 or less. It may be further adjusted within the following ranges.
[72]
In one example, as the polyol, an ester polyol resin may be used. As the ester polyol, for example, an aliphatic ester polyol satisfying the above-mentioned hydroxyl value and/or molecular weight may be used.
[73]
The polyol may be amorphous or a polyol having sufficiently low crystallinity. The term "amorphous" means a case in which the crystallization temperature (Tc) and the melting temperature (Tm) are not observed in differential scanning calorimetry (DSC) analysis. The DSC analysis may be performed at a temperature in 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, then reducing the temperature back to -80 °C, again It can be made in a way that the temperature is raised to 60 ℃. In addition, the sufficiently low crystallinity in the above 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 ° C or less or about -20°C 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.
[74]
In one example, as the ester polyol, for example, a carboxylic acid polyol or a caprolactone polyol may be used.
[75]
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.
[76]
In one example, the polyol may be a polyol represented by the following Chemical Formula 2 or 3.
[77]
[Formula 2]
[78]

[79]
[Formula 3]
[80]

[81]
In Formulas 2 and 3, X is a unit derived from a carboxylic acid, and Y is a unit derived from a polyol. The polyol-derived unit may be, for example, a triol unit or a diol unit. Further, 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, and R 1 and R 2 are each independently 1 to 14 carbon atoms. It may be an alkylene within the range of.
[82]
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.
[83]
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.
[84]
Y in Formula 3 also represents a portion excluding the ester bond after the polyol forms an ester bond with caprolactone. That is, in Formula 3, 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 2 and 3, respectively.
[85]
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.
[86]
In Formula 2, 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 two It may be a unit derived from at least one compound selected from the group consisting of aliphatic compounds having at least one carboxyl group.
[87]
The aromatic compound having two or more carboxyl groups may be, for example, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or tetrachlorophthalic acid.
[88]
The alicyclic compound having two or more carboxyl groups may be, for example, tetrahydrophthalic acid or hexahydrophthalic acid.
[89]
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-dimethylsuccinic acid, 3,3-dimethylglutaric acid, 2,2-dimethylglutaric acid, maleic acid, fumaric acid or itaconic acid.
[90]
Considering the glass transition temperature of the polyol, an aliphatic carboxylic acid-derived unit may be preferable rather than an aromatic carboxylic acid-derived unit.
[91]
In Formulas 2 and 3, the type of the polyol-derived unit of Y is not particularly limited, but in order to secure desired physical properties, it is selected from the group consisting of an alicyclic compound having two or more hydroxyl groups and an aliphatic compound having two or more hydroxyl groups. It may be derived from one or more compounds.
[92]
The alicyclic compound having two or more hydroxyl groups may be, for example, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol.
[93]
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 trimethylolpropanyl can
[94]
In Formula 2, n is an arbitrary number, and the range may be selected in consideration of desired physical properties of the curable composition or a resin layer that is a cured product thereof. For example, n can be about 2 to 10 or 2 to 5.
[95]
In Formula 3, m is an arbitrary number, and the range may be selected in consideration of desired physical properties of the curable composition or a resin layer that is a cured product thereof. For example, m may be about 1 to 10 or 1 to 5.
[96]
When n and m in Chemical Formulas 2 and 3 are out of the above ranges, the crystallinity of the polyol may be strengthened and adversely affect the injection processability of the composition.
[97]
In Formula 3, R 1 and R 2 are each independently alkylene having 1 to 14 carbon atoms. The number of carbon atoms may be selected in consideration of desired physical properties of the curable composition or a resin layer that is a cured product thereof.
[98]
As a reaction inhibitor contained in a curable composition, the compound which has a reaction inhibitory functional group can be used. The term reaction inhibitory functional group means a functional group capable of delaying or inhibiting the reaction of the main resin and the curing agent, for example, exhibiting a higher reactivity with the curing agent compared to the main resin, or with the main resin compared to the curing agent. It may mean a functional group exhibiting higher reactivity. The type of the reaction-inhibiting functional group is determined depending on the type of the main resin and/or the curing agent. For example, when the main resin is a polyol and the curing agent is an isocyanate compound, the reaction inhibiting functional group may be a mercapto group, an amino group, and/or a phenolic hydroxyl group. Such a functional group exhibits a higher reactivity with respect to the isocyanate compound compared to the polyol, and thus a desired waiting time may be secured.
[99]
In one example, as the reaction inhibitor, a compound having a reaction inhibitory functional value in the range of 0.001 to 0.02 according to Formula 2 may be used.
[100]
[Equation 2]
[101]
FV = F/M
[102]
In Formula 2, FV is the reaction inhibitory functional group, F is the number (number of moles) of reaction inhibitory functional groups present in the reaction inhibitor, and M is the molar mass of the reaction inhibitor.
[103]
Through the use of the reaction inhibitor having the reaction inhibitory functional group, it is possible to efficiently achieve a suitable waiting time and a desired curing rate after the elapse of the waiting time.
[104]
In another example, the functional group is 0.002 or more, 0.003 or more, 0.004 or more, or 0.0045 or more, and/or 0.015 or less, 0.01 or less, 0.009 or less, 0.008 or less, 0.007 or less, 0.006 or less, or 0.0055 or less. can
[105]
In Equation 2, M may be in the range of about 50 to 400 g/mol in one example. In another example, M is about 60 g / mol or more, 70 g / mol or more, 80 g / mol or more, 90 g / mol or more, 100 g / mol or more, 110 g / mol or more, 120 g / mol or more, 130 g / mol or more, 140 g / mol or more, 150 g/mol or more, 160 g/mol or more, 170 g/mol or more, 180 g/mol or more, 190 g/mol or more or 195 g/mol or more and/or 390 g/mol or less, 380 g/mol or less, 370 g/mol or less , 360 g/mol or less, 350 g/mol or less, 340 g/mol or less, 330 g/mol or less, 320 g/mol or less, 310 g/mol or less, 300 g/mol or less, 290 g/mol or less, 280 g/mol or less, 270 g/mol or less , 260 g/mol or less, 250 g/mol or less, 240 g/mol or less, 230 g/mol or less, 220 g/mol or less, 210 g/mol or less, 200 g/mol or less, 190 g/mol or less, 180 g/mol or less, 170 g/mol or less , 160 g/mol or less, 150 g/mol or less, 140 g/mol or less, 130 g/mol or less, 120 g/mol or less, or 110 g/mol or less.
[106]
As a suitable reaction inhibitor, a compound having a mercapto group among the functional groups may be used, for example, a compound represented by the following Chemical Formula 1 may be used. In particular, a compound having the above functional group and/or molar mass among the compounds of Formula 1 may be used.
[107]
[Formula 1]
[108]

[109]
In Formula 1, R 1 may represent an alkyl group, an alkoxy group, an aromatic hydrocarbon group, or -Si(R 3 ) 3 . In the above, R 3 may be each independently an alkyl group or an alkoxy group. In Formula 1, R 2 may be a single bond or an alkylene group.
[110]
In Formula 1, the alkyl group, alkoxy group or alkylene group may be an alkyl group, alkoxy group or alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group, alkoxy group or alkylene group may be linear, branched or cyclic.
[111]
In the formula (1), 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 and a zolyl group, an oxadiazolyl group, a thiadiazolyl group, or a dibenzofuranyl group, but is not limited thereto.
[112]
In Formula 1, a single bond refers to a case in which atomic groups on both sides are directly bonded without a separate atom as a mediator.
[113]
The alkyl group, alkoxy group, alkylene group, or aromatic hydrocarbon group of Formula 1 may be optionally substituted with one or more substituents. In this case, the substituent may include, but is not limited to, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, or a mercapto group.
[114]
As another example, in Formula 1, R 1 is an alkyl group having 1 to 4 carbon atoms or an unsubstituted or unsubstituted 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 1, 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.
[115]
In one example, the compound represented by Formula 1 may have only one mercapto group as the reaction inhibitory functional group. Therefore, in Formula 1, R 1 and R 2 may not include a mercapto group (-SH) and other reaction-inhibiting functional groups.
[116]
The content of the reaction inhibitor in the curable composition may be controlled in a range suitable for securing a desired curing rate and the like. In one example, the reaction inhibitor may be present in an amount of about 0.05 to 0.5 parts by weight within 100 parts by weight of the curable composition. A total of 100 parts by weight of the curable composition is in the range defined by excluding the weight of the component to be removed when the curable composition includes a component to be finally removed such as a solvent. In addition, the total 100 parts by weight is a range stipulated based on the weight of the composition when the curable composition is a one-component type, and in the case of a two-component type, the weight of the main composition, the weight of the curing agent composition, or the sum of the main agent and the curing agent composition It is a range obtained based on the weight.

WE CLAIMS

[Claim 1]The difference between Shore A Hardness 90 Check Time (H t90 ) and Shore A Hardness 40 Check Time (H t40 ) according to ASTM D 2240 (H t90 -H t40 ) is 200 minutes , including polyols, inhibitors, catalysts and fillers. The following curable compositions.
[Claim 2]
The curable composition according to claim 1, wherein the Shore A hardness 90 confirmation time according to ASTM D 2240 is in the range of 70 minutes to 400 minutes.
[Claim 3]
The curable composition according to claim 1, wherein the Shore A hardness 40 confirmation time (H t40 ) according to ASTM D 2240 is in the range of 40 minutes to 300 minutes.
[Claim 4]
The method according to claim 1, wherein the difference (H t40 -H ti ) between the Shore A hardness confirmation time (Ht i ) and the Shore A hardness 40 confirmation time (H t40 ) according to ASTM D 2240 is 1 minute to 30 minutes. curable composition within the range.
[Claim 5]
The curable composition according to claim 1, wherein the reaction inhibitor comprises at least one reaction inhibitory functional group selected from the group consisting of a mercapto group, an amino group, and a phenolic hydroxyl group.
[Claim 6]
[Claim 6] The curable composition according to claim 5, wherein the reaction inhibitor has a reaction inhibitory functional value according to the following formula 2 in the range of 0.001 to 0.02: [Formula 2] FV = F/M In formula 2, FV is the reaction inhibitory functional group , F is the number of the reaction inhibitory functional group, M is the molar mass of the reaction inhibitor.
[Claim 7]
The curable composition according to claim 1, wherein the reaction inhibitor is present such that R1 of the following formula 3 is in the range of 2 to 30: [Formula 3] R1 = (W1×O/M)-(FV×W2) O in Formula 3 is the hydroxyl value of the polyol, M is the weight average molecular weight of the polyol, FV is the reaction inhibitory functional group of the reaction inhibitor, W1 is the weight ratio of the reaction inhibitor to the reaction inhibitor of the polyol, W2 is the reaction inhibitor It is a weight ratio to polyol.
[Claim 8]
The curable composition according to claim 1, wherein the weight ratio (IW/CW) of the reaction inhibitor (IW) and the catalyst (CW) is in the range of 1.3 to 4.
[Claim 9]
The curable composition according to claim 1, comprising 70 to 95% by weight of the filler.
[Claim 10]
The curable composition of claim 1, further comprising an isocyanate compound.
[Claim 11]
The curable composition according to claim 10, wherein the isocyanate compound has an isocyanate valency in the range of 0.001 to 0.1 according to Formula 4: [Formula 4] NCOV = NCO/MN In Formula 4, NCOV is the isocyanate, and NCO is the isocyanate It is the number (number of moles) of isocyanate groups which a compound has, and MN is the molar mass of the said isocyanate compound.
[Claim 12]
The curable composition according to claim 10, wherein the isocyanate compound is present such that R2 of the following formula 5 is in the range of 10 to 150: [Formula 5] R2 = (W1×O/M)/(NCOV×W3) O in Formula 5 is the hydroxyl value of the polyol, NCOV is the isocyanate number of the isocyanate compound, W1 is the weight ratio of the polyol to the isocyanate compound, and W3 is the weight ratio of the isocyanate compound to the polyol.
[Claim 13]
The curable composition according to claim 10, wherein the isocyanate compound is present such that R3 of the following Formula 6 is in the range of 50 to 500: [Formula 6] R3 = (FV×W2)/(NCOV×W3) In Formula 6, FV is the reaction is the reaction inhibitory functional group of the inhibitor, NCOV is the isocyanate number of the isocyanate compound, W2 is the weight ratio of the reaction inhibitor to the isocyanate compound, and W3 is the weight ratio of the isocyanate compound to the reaction inhibitor.
[Claim 14]
a module case having an interior space; a plurality of battery cells existing in the inner space of the module case; and a resin layer comprising a cured product of the curable composition of claim 1, wherein the resin layer is present in the inner space in contact with the plurality of battery cells and the module case.
[Claim 15]
A battery pack comprising two or more of the battery modules of claim 14, which are electrically connected to each other.