Curable composition

Abstract

To provide a curable composition which causes less viscosity change by time, is excellent in compounding property with a filler, can secure process property, and enables formation of a cured product having excellent electric insulation performance, and a device including a cured product of a two-pack type curable composition containing a curable composition for bringing a heat generating element and a cooling part into thermal contact with each other.SOLUTION: A curable composition contains a resin component containing a polyfunctional isocyanate compound and a bifunctional isocyanate compound, and a filler.SELECTED DRAWING: None

Description

Technical Field

[0001] Cross-reference to Related Applications This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0017008 filed on February 5, 2021 and Korean Patent Application No. 10-2022-0003898 filed on January 11, 2022, and all contents disclosed in the documents of the Korean patent applications are included as part of this application.

[0002] Technical Field This application relates to a curable composition and its use.

Background Art

[0003] The treatment of heat generated from batteries such as electrical products, electronic products, or secondary batteries has become an important issue, and various heat dissipation measures have been proposed. Among the heat conductive materials used for heat dissipation measures, a curable composition in which a heat conductive filler is blended with a resin component is known. Patent Document 1 discloses a battery module to which a cured product of such a curable composition is applied.

[0004] The curable composition is required to have a low viscosity change over time to ensure processability, and the cured product of the curable composition is required to have electrical insulation performance for safety and for protecting elements of batteries such as electrical products, electronic products, or secondary batteries.

[0005] In order for the cured product of the curable composition to have excellent electrical insulation performance, the volume resistivity must be increased. To increase the volume resistivity, it is advantageous for the cured product to have a high crosslink density. To increase the crosslink density, it is preferable to use a resin component having many functional groups and high reactivity.

[0006] However, when the amount of the resin component having high reactivity is increased, the compatibility with the filler decreases, and there is a problem that the viscosity change over time increases.

[0007] Therefore, there has been a demand for a curable composition that has excellent compatibility with a filler, exhibits little viscosity change over time, and forms a cured product having excellent electrical insulation performance.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present application aims to provide a curable composition that can solve the above-described problems.

[0010] The present application aims to provide a curable composition that exhibits little viscosity change over time, has excellent compatibility with a filler, and can ensure processability.

[0011]

[0012] The present application aims to provide an apparatus including a cured product of a curable composition that thermally contacts a heating element and a cooling part with each other.

Means for Solving the Problems

[0013] In the present application, the normal temperature of the term used means the temperature in a natural state without being particularly heated or cooled, and can mean any temperature within the range of about 10°C to 30°C, for example, a temperature of about 15°C or higher, about 18°C or higher, about 20°C or higher, or about 23°C or higher, or about 27°C or lower.

[0014] As used in this application, the alkyl group or alkylene group of the terms used herein, unless otherwise specified, may be a straight-chain or branched acyclic alkyl group or alkylene group having 1 to 20 carbon atoms, or 1 to 16 carbon atoms, or 1 to 12 carbon atoms, or 1 to 8 carbon atoms, or 1 to 6 carbon atoms, or may be a cyclic alkyl group or alkylene group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms. Here, the cyclic alkyl group or alkylene group includes an alkyl group or alkylene group having only a ring structure and an alkyl group or alkylene group containing a ring structure. For example, both the cyclohexyl group and the methylcyclohexyl group fall within the category of cyclic alkyl groups.

[0015] As used in this application, the alkenyl group or alkenylene group of the terms used herein, unless otherwise specified, may be a straight-chain or branched acyclic alkenyl group or alkenylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms, or 2 to 6 carbon atoms, or may be a cyclic alkenyl group or alkenylene group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms. Here, if it includes an alkenyl group or alkenylene group having a ring structure, it falls within the category of cyclic alkenyl groups or alkenylene groups.

[0016] As used in this application, the alkynyl group or alkynylene group of the terms used herein, unless otherwise specified, may be a straight-chain or branched acyclic alkynyl group or alkynylene group having 2 to 20 carbon atoms, or 2 to 16 carbon atoms, or 2 to 12 carbon atoms, or 2 to 8 carbon atoms, or 2 to 6 carbon atoms, or may be a cyclic alkynyl group or alkynylene group having 3 to 20 carbon atoms, or 3 to 16 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms, or 3 to 6 carbon atoms. Here, if it includes an alkynyl group or alkynylene group having a ring structure, it falls within the category of cyclic alkynyl groups or alkynylene groups.

[0017] The alkyl group, alkylene group, alkenyl group, alkenylene group, alkynyl group, and alkynylene group may be optionally substituted with one or more substituents. In this case, the substituents may be one or more selected from the group consisting of halogen (chloro (Cl), iodine (I), bromo (Br), fluoro (F)), aryl group, heteroaryl group, ether group, carbonyl group, carboxyl group, and hydroxy group, but are not limited thereto.

[0018] As used in this application, the term "aryl group" may mean an aromatic ring from which one hydrogen has been removed from an aromatic hydrocarbon ring, unless otherwise specified. The aryl group may be monocyclic or polycyclic.

[0019] As used in this application, the term "heteroaryl group" may mean a substituent containing an aromatic ring containing one or more heteroatoms (e.g., N, O, S, etc.) as atoms forming the ring, unless otherwise specified. The heteroaryl group may be monocyclic or polycyclic.

[0020] As used in this application, the term "weight average molecular weight" basically means the representative molecular weight of a polymer compound, but may also mean the molar molecular weight of a compound that is not a polymer compound.

[0021] The curable composition of this application may be a heat dissipation composition. As used in this application, the term "heat dissipation composition" means a composition capable of forming a cured product having heat dissipation performance. Also, as used in this application, the term "heat dissipation performance" may mean a case where the cured product of the heat dissipation composition prepared with a thickness of 4 mm exhibits a thermal conductivity of about 2.5 W / m·K or more when measured in the thickness direction according to ASTM D5470 standard or ISO 22007-2 standard.

[0022] In other examples, the thermal conductivity may be about 2.6 W / m·K or more, 2.7 W / m·K or more, 2.8 W / m·K or more, 2.9 W / m·K or more, or 3.0 W / m·K or more. Since a higher value of the thermal conductivity means higher thermal conductivity, its upper limit is not particularly limited. For example, the thermal conductivity may be 20 W / m·K or less, 18 W / m·K or less, 16 W / m·K or less, 14 W / m·K or less, 12 W / m·K or less, 10 W / m·K or less, 8 W / m·K or less, 6 W / m·K or less, or 4 W / m·K or less.

[0023] The curable composition according to an example of the present application contains a resin component and a filler.

[0024] The term "resin component" as used in the present application includes not only components generally known as resins but also components that can be converted into resins through a curing reaction or a polymerization reaction. In one example, as the resin component, an adhesive resin or a precursor capable of forming an adhesive resin may be applied. Examples of such resin components include acrylic resins, epoxy resins, urethane resins, olefin resins, EVA (ethylene vinyl acetate) resins, or silicone resins, and precursors such as polyol or isocyanate compounds, but are not limited thereto.

[0025] The term "curable composition" as used in the present application also includes not only components generally known as resins but also components that can be converted into resins through a curing reaction or a polymerization reaction. Further, the curable composition may be an adhesive composition, that is, it may be an adhesive itself or a composition capable of forming an adhesive through a reaction such as a curing reaction. Such a curable composition may be a solvent-based curable composition, an aqueous curable composition, or a solventless curable composition.

[0026] Also, the curable composition may be a one-component curable composition or a two-component curable composition.

[0027] As used in this application, the term one-component curable composition means a composition that can form a resin by reacting when it satisfies specific conditions (e.g., specific temperature or ultraviolet irradiation, etc.) in a state where the main agent part and the curing agent part are mixed, as is known.

[0028] Also, as used in this application, the term two-component curable composition means a composition that is separated into a main agent part and a curing agent part, and can form a resin by mixing and reacting these two separated parts, as is known.

[0029] The curable composition according to an example of this application can refer to the main agent part, the curing agent part, a mixture thereof, or the state after mixing them and undergoing a reaction.

[0030] The two-component curable composition according to an example of this application may be a urethane composition or a two-component urethane composition. The two-component urethane composition may include a main agent part containing a resin component including a polyol and a curing agent part containing a resin component including an isocyanate compound.

[0031] The curable composition according to an example of this application may include a resin component including a polyfunctional isocyanate compound and a bifunctional isocyanate compound, and a filler.

[0032] The polyfunctional isocyanate compound may mean a compound containing 3 or more isocyanate groups. In other examples, the polyfunctional isocyanate compound may mean a compound containing 3 to 10, 3 to 9, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 3 to 4, or 3 isocyanate groups.

[0033] The bifunctional isocyanate compound may mean a compound containing 2 isocyanate groups.

[0034] The resin component of the curable composition according to an example of the present application may have a weight average molecular weight of 400 g / mol or more, 440 g / mol or more, 480 g / mol or more, 520 g / mol or more, 560 g / mol or more, or 600 g / mol or more. In other examples, the resin component may have a weight average molecular weight of 1,000 g / mol or less, 960 g / mol or less, 920 g / mol or less, 880 g / mol or less, 840 g / mol or less, or 800 g / mol or less. Here, the weight average molecular weight of the resin component may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0035] Also, the resin component of the curable composition according to an example of the present application may have a polydispersity index (PDI) of 1.2 or more, 1.25 or more, 1.3 or more, 1.35 or more, or 1.4 or more. In other examples, the resin component may have a polydispersity index of 1.8 or less, 1.75 or less, 1.7 or less, 1.65 or less, or 1.6 or less. Here, the polydispersity index of the resin component may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0036] Here, the weight average molecular weight and the number average molecular weight of the resin component can be measured using gel permeation chromatography (GPC). Specifically, the resin component is placed in a 20 mL vial and diluted with a THF (tetrahydrofuran) solvent to a concentration of about 20 mg / mL. After filtering the calibration standard sample and the resin component with a syringe filter (pore size: 0.2 μm), the weight average molecular weight and the number average molecular weight of the resin component are measured using a measuring instrument (1200 series from Agilent technologies). At this time, the columns used were TL Mix.A&B from Agilent technologies, and the standard samples used were MP: 364000, 91450, 17970, 4910, 1300.

[0037] The polydispersity index of the resin component can be calculated using the weight-average molecular weight and the number-average molecular weight measured by the gel permeation chromatography, and the polydispersity index can be defined as the value obtained by dividing the weight-average molecular weight by the number-average molecular weight.

[0038] The resin component of the curable composition according to an example of the present application may have a K value of 0.4 or more according to the following formula 1. In other examples, the resin component may have a K value of 0.425 or more, 0.45 or more, 0.475 or more, 0.5 or more, 0.525 or more, 0.5 or more, 0.575 or more, 0.6 or more, or 0.625 or more according to the following formula 1. In still other examples, the resin component may have a K value of 1.8 or less, 1.75 or less, 1.7 or less, 1.65 or less, 1.6 or less, 1.55 or less, or 1.5 or less according to the following formula 1. Here, the K value of the resin component according to the following formula 1 may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0039] When the K value of the resin component according to the following formula 1 satisfies the above range, when compounded with a filler, a curable composition may be formed that has excellent compatibility and little change in viscosity of the curable composition after compounding, and the cured product has excellent electrical insulation performance. When the K value of the resin component according to the following formula 1 is less than the lower limit, when compounded with a filler, the compounding may be poor and the viscosity of the curable composition after compounding may increase rapidly.

[0040] [Formula 1] K = Σ(N×W)

[0041] In formula 1, N is a value obtained by the following formula 2 for each individual isocyanate compound contained in the resin component, and W is the content (unit: weight%) of the individual isocyanate compound based on the total amount of isocyanate compounds contained in the resin component.

[0042] [Formula 2] N = F / M

[0043] In Formula 2, F is the number of isocyanate groups that the individual isocyanate compound has, and M is the weight average molecular weight (unit: g / mol) of the individual isocyanate compound. The weight average molecular weight can be measured using gel permeation chromatography (GPC). Further, M may be, as necessary, the molar mass (unit: g / mol) of the individual isocyanate compound.

[0044] The resin component of the curable composition according to an example of the present application may contain a bifunctional isocyanate compound in an amount of 15 parts by weight or more, 17.5 parts by weight or more, 20 parts by weight or more, 22.5 parts by weight or more, or 25 parts by weight or more with respect to 100 parts by weight of the polyfunctional isocyanate compound. In other examples, the resin component may contain a bifunctional isocyanate compound in an amount of 80 parts by weight or less, 76 parts by weight or less, 72 parts by weight or less, or 68 parts by weight or less with respect to 100 parts by weight of the polyfunctional isocyanate compound. Here, the content of the bifunctional isocyanate compound in the resin component may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0045] When the content of the bifunctional isocyanate compound in the resin component satisfies the above range, a curable composition having excellent compatibility and little change in viscosity of the curable composition after blending may be formed so that the cured product has excellent electrical insulation performance when blended with a filler.

[0046] The resin component of the curable composition according to an example of the present application may have a room temperature viscosity of 400 cP or more, 420 cP or more, 440 cP or more, 460 cP or more, or 480 cP or more as measured at room temperature. In other examples, the resin component of the curable composition may have a room temperature viscosity of 600 cP or less, 580 cP or less, 560 cP or less, 540 cP or less, or 520 cP or less. At this time, the viscosity of the resin component may be a value measured using a viscosity measuring device (manufacturer: Brookfield, model name: Brookfield LV) and a spindle LV-63, or may be a value measured with a rotational speed of 20 rpm or 100 rpm during viscosity measurement. Here, the room temperature viscosity of the resin component may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0047] When the viscosity of the resin component satisfies the above range, it has excellent compatibility with the filler, can ensure processability, and has little viscosity change even after mixing with the filler.

[0048] The resin component of the curable composition according to an example of the present application may contain a polyfunctional isocyanate compound having a weight average molecular weight of 600 g / mol or more, 650 g / mol or more, 700 g / mol or more, 750 g / mol or more, or 800 g / mol or more. In other examples, the resin component may contain a polyfunctional isocyanate compound having a weight average molecular weight of 2,000 g / mol or less, 1,500 g / mol or less, 1,000 g / mol or less, or 850 g / mol or less. Here, the weight average molecular weight of the polyfunctional isocyanate compound may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0049] Also, the resin component of the curable composition according to an example of the present application may contain a polyfunctional isocyanate compound having a polydispersity index (PDI) of 0.8 or more, 0.85 or more, 0.9 or more, 0.95 or more, or 1 or more. In another example, the resin component may contain a polyfunctional isocyanate compound having a polydispersity index of 1.5 or less, 1.45 or less, 1.4 or less, 1.35 or less, 1.3 or less, 1.25 or less, or 1.2 or less. The polydispersity index of the polyfunctional isocyanate compound may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0050] The resin component of the curable composition according to an example of the present application may contain a bifunctional isocyanate compound having a weight average molecular weight of 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, or 170 g / mol or more. In another example, the resin component may contain a bifunctional isocyanate compound having a weight average molecular weight of 500 g / mol or less, 450 g / mol or less, 400 g / mol or less, 350 g / mol or less, 300 g / mol or less, or 250 g / mol or less. Here, the weight average molecular weight of the bifunctional isocyanate compound may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0051] Also, the resin component according to an example of the present application may contain a bifunctional isocyanate compound having a polydispersity index (PDI) of 0.8 or more, 0.85 or more, 0.9 or more, 0.95 or more, or 1 or more. In another example, the resin component may contain a bifunctional isocyanate compound having a polydispersity index of 1.4 or less, 1.35 or less, 1.3 or less, 1.25 or less, 1.2 or less, 1.15 or less, or 1.1 or less. Here, the polydispersity index of the bifunctional isocyanate compound may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0052] Here, the weight average molecular weight and number average molecular weight of the polyfunctional isocyanate compound and bifunctional isocyanate compound of the resin component can be measured using gel permeation chromatography (GPC) in the same manner as the measurement method for the weight average molecular weight and number average molecular weight of the resin component.

[0053] The bifunctional isocyanate compound according to an example of the present application is not particularly limited as long as it contains two isocyanate groups, and a bifunctional isocyanate compound mainly used in the industry may be used.

[0054] Examples of the bifunctional isocyanate compound include aromatic bifunctional isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polyethylene phenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate; aliphatic bifunctional isocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate, or tetramethylene diisocyanate; or alicyclic bifunctional isocyanates such as trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane diisocyanate, or dicyclohexylmethane diisocyanate. The application of polyisocyanates other than aromatic ones is appropriate to ensure the desired physical properties.

[0055] The bifunctional isocyanate compound according to an example of the present application may be a compound represented by the following Chemical Formula 1.

[0056]

Chemical Formula

[0057] In Chemical Formula 1, L1 may contain a linear or branched alkylene group, a cyclic alkylene group, a cyclic alkenylene group, or a cyclic alkynyl group. Specifically, L1 may contain a linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms, a cyclic alkenylene group having 3 to 20 carbon atoms, or a cyclic alkynyl group having 3 to 20 carbon atoms.

[0058] In Chemical Formula 1, L1 is represented by the following Chemical Formula 2.

[0059]

Chemical Formula

[0060] In Chemical Formula 2, P1 is a cyclic alkylene group having 3 to 20 carbon atoms substituted with one or more alkyl groups, and L2 and L3 may each independently be a single bond or an alkylene group having 1 to 10 carbon atoms.

[0061] Also, in Chemical Formula 2, L2 and L3 may each independently be a single bond or an alkylene group having 1 to 8 carbon atoms, and in other examples, may each independently be a single bond or an alkylene group having 1 to 4 carbon atoms.

[0062] Also, in Chemical Formula 1, L1 is represented by the following Chemical Formula 3.

[0063]

Chemical Formula

[0064] In Chemical Formula 3, P2 and P3 are each independently a cyclic alkylene group having 3 to 20 carbon atoms, L4 and L6 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, and L5 may be an alkylene group having 1 to 10 carbon atoms.

[0065] Alternatively, in Chemical Formula 3, L4 and L6 may each independently be a single bond or an alkylene group having 1 to 8 carbon atoms, and in other examples, may each independently be a single bond or an alkylene group having 1 to 4 carbon atoms.

[0066] Further, in Chemical Formula 3, L5 may be an alkylene group having 1 to 8 carbon atoms, and in other examples, may be a single bond or an alkylene group having 1 to 4 carbon atoms.

[0067] The polyfunctional isocyanate compound according to an example of the present application is not particularly limited as long as it contains 3 or more isocyanate groups, and a trifunctional isocyanate compound mainly used in the industry or an isocyanate compound containing 3 or more isocyanate groups may be used.

[0068] At least one selected from multimers of the bifunctional isocyanate compound may be used as the polyfunctional isocyanate compound. Specifically, as the polyfunctional isocyanate compound, aromatic bifunctional isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polyethylene phenylene polyisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolidine diisocyanate, and naphthalene diisocyanate, aliphatic bifunctional isocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate, or tetramethylene diisocyanate, or alicyclic bifunctional isocyanates such as trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane diisocyanate, or dicyclohexylmethane diisocyanate may be used, but the present invention is not limited thereto.

[0069] The polyfunctional isocyanate compound according to an example of the present application may be a trifunctional isocyanate compound, and when it is a trifunctional isocyanate compound, it may be a compound represented by the following Chemical Formula 4.

[0070]

Chemical Formula

[0071] In Chemical Formula 4, L7, L8, and L9 may each independently be an alkylene group, an alkenylene group, or an alkynyl group. Specifically, L7, L8, and L9 may each independently be an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms.

[0072] The filler of the curable composition according to an example of the present application may be included, for example, for ensuring thixotropy and / or ensuring heat dissipation (thermal conductivity) in a battery module or a battery pack as required in the process.

[0073] As described later, the curable composition may contain an excessive amount of filler. When an excessive amount of filler is used, the viscosity of the curable composition increases, and the processability may deteriorate when injecting the composition into the case of the battery module. Therefore, while containing an excessive amount of filler, it is necessary to have a sufficiently low viscosity property so as not to hinder the processability. Also, if only a low viscosity is exhibited, it is still difficult to ensure the processability, so an appropriate thixotropy is required, and it is necessary to show a desired appropriate adhesive force while curing, and the curing itself is performed at room temperature.

[0074] In particular, in order to form a cured product having excellent electrical insulation performance, it is advantageous to use a resin component having many functional groups and high reactivity. However, when the amount of the resin component having high reactivity is increased, the compatibility with the filler decreases, and a problem occurs in that the viscosity change over time increases.

[0075] The curable composition according to an example of the present application uses a resin component suitable for forming a cured product having excellent electrical insulation performance, while ensuring the processability described above, having little viscosity change over time, and the resin component and filler are appropriately combined and selected so that the cured product has heat dissipation performance.

[0076] The filler may be a thermally conductive filler, and this thermally conductive filler is a filler capable of forming a cured product having a thermal conductivity as described above.

[0077] The thermal conductivity of the thermally conductive filler itself may be, for example, 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. In other examples, the thermal conductivity of the thermally conductive filler itself may be, for example, about 400 W / mK or less, about 350 W / mK or less, or about 300 W / mK or less.

[0078] Examples of the thermally conductive filler include oxides such as aluminum oxide (alumina), magnesium oxide, beryllium oxide or titanium oxide, nitrides such as boron nitride, silicon nitride or aluminum nitride, carbides such as silicon carbide, hydrated metals such as aluminum hydroxide or magnesium hydroxide, metal fillers such as copper, silver, iron, aluminum or nickel, metal alloy fillers such as titanium, and silicon powders such as quartz, glass or silica, but are not limited thereto.

[0079] Also, if insulation properties can be ensured, the application of carbon fillers such as graphite can also be considered. For example, activated carbon may be used as the carbon filler. The form and ratio of the filler contained in the cured product are not particularly limited, and may be selected in consideration of the viscosity of the curable composition, the possibility of sedimentation in the cured product, the desired thermal resistance or thermal conductivity, insulation properties, filling effect or dispersibility.

[0080] The shape of the thermal conductive filler may be appropriately selected and used as needed from spherical and / or non-spherical shapes (for example, needle-like and plate-like shapes, etc.), and is not limited thereto.

[0081] In this application, the term spherical particles means particles with a sphericity of about 0.95 or more, and non-spherical particles means particles with a sphericity of less than 0.95.

[0082] The sphericity can be confirmed through particle size analysis of the particles. Specifically, the sphericity of a filler that is a three-dimensional particle is defined as the ratio (S’ / S) of the surface area (S) of the particle to the surface area (S’) of a sphere having the same volume as the particle. For actual particles, generally circularity is used. The circularity is obtained by obtaining a two-dimensional image of the actual particle and representing it as the ratio of the boundary of a circle having the same area (A) as the image to the boundary of the image, and is obtained by the following formula.

[0083] <Circularity formula> Circularity = 4πA / P 2

[0084] The circularity is represented by a value from 0 to 1. A perfect circle has a value of 1, and the more irregular the shape of the particle, the lower the value will be compared to 1. The sphericity value in this specification was taken as the average value of the circularity measured by a particle size analysis instrument (FPIA-3000) manufactured by Marvern.

[0085] One or more types of thermal conductive fillers appropriately selected as needed may be used. Also, even if the same type of thermal conductive filler is used, those with different shapes may be mixed and used, or those with different average particle sizes may be mixed and used. For example, aluminum hydroxide, aluminum, and alumina may be mixed and used as a thermal conductive filler, and their shapes and average particle sizes may be different from each other.

[0086] Also, considering the amount to be filled, it is advantageous to use spherical thermal conductive fillers. However, considering the formation of the network and conductivity, etc., thermal conductive fillers in the form of needles or plates may also be used.

[0087] In one example, the curable composition may contain a thermal conductive filler having an average particle size in the range of 0.001 μm to 100 μm. The average particle size of the thermal conductive filler may be 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 other examples. The average particle size of the thermal conductive filler may be about 95 μm or less, about 90 μm or less, about 85 μm or less, about 80 μm or less, about 75 μm or less, about 70 μm or less, about 65 μm or less, about 60 μm or less, about 55 μm or less, about 50 μm or less, about 45 μm or less, about 40 μm or less, about 35 μm or less, about 30 μm or less, about 25 μm or less, about 20 μm or less, about 15 μm or less, about 10 μm or less, or about 5 μm or less in other examples.

[0088] At this time, the average particle size of the thermal conductive filler can mean the particle size at 50% cumulative volume basis of the particle size distribution as the so-called D50 particle size (median particle size). That is, the particle size distribution is determined on a volume basis, and in the cumulative curve with the total volume as 100%, the particle size at the point where the cumulative value becomes 50% can be said to be the average particle size. The D50 particle size as described above may be measured by the laser diffraction method.

[0089] In order to obtain excellent heat dissipation performance, it is conceivable to use a filler in a high content in the curable composition of the present application. Further, considering not only ensuring excellent heat dissipation performance as described above but also ensuring processability, the content of the filler in the curable composition of the present application may be 80% by weight or more, 82.5% by weight or more, 85% by weight or more, or 87.5% by weight or more based on the total weight of the curable composition. In other examples, the content of the filler may be 95% by weight or less, 92.5% by weight or less, or 90% by weight or less based on the total weight of the curable composition. Here, the content of the filler may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0090] The curable composition according to the present application may further contain the following additives.

[0091] The curable composition according to the present application may further contain a plasticizer as needed. The type of the plasticizer is not particularly limited. For example, one or more may be selected from phthalic acid compounds, phosphoric acid compounds, adipic acid compounds, sebacic acid compounds, citric acid compounds, glycolic acid compounds, trimellitic acid compounds, polyester compounds, epoxidized soybean oil, chlorinated paraffin, chlorinated fatty acid esters, fatty acid compounds, compounds having a saturated aliphatic chain substituted with a sulfonic acid group bonded with a phenyl group (for example, mesamoll of LANXESS), and vegetable oils and used.

[0092] As the phthalic acid compound, one or more of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate, butyl octyl phthalate, octyl benzyl phthalate, n-hexyl n-decyl phthalate, n-octyl phthalate, and n-decyl phthalate may be used.

[0093] The phosphoric acid compound may use one or more of tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, octyldiphenyl phosphate, cresyldiphenyl phosphate, and trichloroethyl phosphate.

[0094] The adipic acid compound may use one or more of dibutoxyethoxyethyl adipate (DBEEA), dioctyl adipate, diisooctyl adipate, di-n-octyl adipate, didecyl adipate, diisodecyl adipate, n-octyl n-decyl adipate, n-heptyl adipate, and n-nonyl adipate.

[0095] The sebacic acid compound may use one or more of dibutyl sebacate, dioctyl sebacate, diisooctyl sebacate, and butyl benzyl sebacate.

[0096] The citric acid compound may use one or more of triethyl citrate, acetyltriethyl citrate, tributyl citrate, acetyltributyl citrate, and acetyltrioctyl citrate.

[0097] The glycolic acid compound may use one or more of methylphtharylethyl glycolate, ethylphtharylethyl glycolate, and butylphtharylethyl glycolate.

[0098] The trimellitic acid compound may use one or more of trioctyl trimellitate and tri-n-octyl n-decyl trimellitate.

[0099] In addition, the curable composition according to the present application may further contain a viscosity modifier, for example, a thixotropy-imparting agent, a diluent, a surface treatment agent, or a coupling agent, etc., as necessary, for adjusting the viscosity, for example, increasing or decreasing the viscosity, or for adjusting the viscosity by shear force. The thixotropy-imparting agent can adjust the viscosity of the curable composition by shear force. Examples of the thixotropy-imparting agent that can be used include fumed silica. The diluent is usually used to lower the viscosity of the curable composition, and various types known in the industry may be used without limitation as long as they can exhibit the above-described effects. The surface treatment agent is for surface treatment of the filler introduced into the cured product of the curable composition, and various types known in the industry may be used without limitation as long as they can exhibit the above-described effects. In the case of a coupling agent, for example, it may be used to improve the dispersibility of a heat-conductive filler such as alumina, and various types known in the industry may be used without limitation as long as they can exhibit the above-described effects.

[0100] Furthermore, the curable composition according to the present application may further contain a flame retardant or a flame retardant aid, etc., as necessary. The curable composition containing a flame retardant or a flame retardant aid, etc., can be cured to form a flame-retardant resin. As the flame retardant, various known flame retardants may be applied without particular limitation, and for example, a flame retardant in the form of a solid-phase filler or a liquid flame retardant may be applied. Examples of the flame retardant include, but are not limited to, organic flame retardants such as melamine cynaurate and inorganic flame retardants such as magnesium hydroxide. When the amount of the heat-conductive filler contained in the curable composition is large, a liquid-type flame retardant material (such as TEP, triethyl phosphate or TCPP, tris(1,3-chloro-2-propyl) phosphate, etc.) may be used. Also, a silane coupling agent that can act as a flame retardancy enhancer may be added.

[0101] The curable composition may include the configuration as described above, and may be a solvent-based composition, an aqueous composition, or a solvent-free composition. However, considering the convenience of the manufacturing process described later, etc., a solvent-free type is appropriate.

[0102] When the viscosity of the curable composition satisfies the above range, workability can be ensured and productivity can be improved.

[0103] The curable composition according to an example of the present application may have a viscosity change rate after 12 days according to the following formula 3 of 0.5 or more, 0.55 or more, 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, or 0.8 or more. In other examples, the curable composition may have a viscosity change rate after 12 days according to the following formula 3 of 1.6 or less, 1.55 or less, 1.5 or less, 1.45 or less, 1.4 or less, 1.35 or less, 1.3 or less, 1.25 or less, or 1.2 or less. Here, the viscosity change rate after 12 days of the curable composition according to the following formula 3 may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0104] [Formula 3] Viscosity change rate after 12 days = μ f / μ i

[0105] The above μ f is the viscosity measured after leaving the curable composition at room temperature for 12 days, The above μ i is the viscosity of the curable composition before leaving it at room temperature for 12 days.

[0106] At this time, μ i and μ f may be the room temperature viscosity measured in the same manner as the following room temperature viscosity measurement method.

[0107] The viscosity of the curable composition may be a value measured using a viscometer (manufacturer: Brookfield, model name: DV3THB-CP) and a spindle CPA-52Z, or may be a value measured after rotating for 180 seconds with a shear rate of 2.4 / s.

[0108] The two-component curable composition according to an example of the present application may include a main agent part and a curing agent part. The main agent part contains polyol, and the curing agent part may contain the curable composition according to an example of the present application.

[0109] The two-component curable composition according to an example of the present application may be a urethane composition. At this time, the two-component curable composition may be a room temperature curable type.

[0110] The polyol according to an example of the present application means a compound containing two or more hydroxy groups, such as (poly)ethylene glycol, diethylene glycol, (poly)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-ethylhexyl diol, 1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, (poly)ethylene triol, diethylene triol, (poly)propylene triol, glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,3,4-hexanetriol, 1,3,6-hexanetriol units and trimethylolpropane, etc., but is not particularly limited thereto.

[0111] The polyol according to an example of the present application includes ester polyol. The ester polyol may include carboxylic acid polyol and / or caprolactone polyol.

[0112] The polyol according to an example of the present application may be a polyol represented by the following Chemical Formula 5 or 6.

[0113]

Chemical Formula

[0114] [Chem.]

[0115] In Chemical Formulas 5 and 6, X is a unit derived from a dicarboxylic acid, Y is a unit derived from a polyol, such as a unit of a triol or a diol, and n and m are arbitrary numbers.

[0116] In the above, the unit derived from a dicarboxylic acid is a unit formed by the urethane reaction of a dicarboxylic acid with a polyol, and the unit derived from a polyol is a unit formed by the urethane reaction of a polyol with a dicarboxylic acid or caprolactone.

[0117] That is, when the hydroxy group of the polyol reacts with the carboxyl group of the dicarboxylic acid, a water (H2O) molecule is eliminated by a condensation reaction to form an ester bond. In Chemical Formula 5 above, X means the portion excluding the ester bond portion after the dicarboxylic acid forms an ester bond by the condensation reaction, and Y is also the portion excluding the ester bond after the polyol forms an ester bond by the condensation reaction. The ester bond is represented by Chemical Formula 5.

[0118] Also, in Chemical Formula 6, Y also indicates the portion excluding the ester bond after the polyol forms an ester bond with caprolactone.

[0119] On the other hand, when the unit derived from the polyol of Y in the above is a unit derived from a polyol containing three or more hydroxy groups such as a triol unit, a structure in which a branch is formed in the Y portion in the structure of the chemical formula may be realized.

[0120] In Chemical Formula 5, the type of the dicarboxylic acid-derived unit of X is not particularly limited, but it may be any unit selected from the group consisting of phthalic acid unit, isophthalic acid unit, terephthalic acid unit, trimellitic acid unit, tetrahydrophthalic acid unit, hexahydrophthalic acid unit, tetrachlorophthalic acid unit, oxalic acid unit, adipic acid unit, azelaic acid unit, sebacic acid unit, succinic acid unit, malic acid unit, glutaric acid unit, malonic acid unit, pimelic acid unit, suberic acid unit, 2,2-dimethylsuccinic acid unit, 3,3-dimethylglutaric acid unit, 2,2-dimethylglutaric acid unit, maleic acid unit, fumaric acid unit, itaconic acid unit, and fatty acid unit in order to ensure the desired physical properties.

[0121] In Chemical Formulas 5 and 6, the type of the polyol-derived unit of Y is not particularly limited, but it may be any one or two or more selected from the group consisting of ethylene glycol unit, propylene glycol unit, 1,2-butylene glycol unit, 2,3-butylene glycol unit, 1,3-propanediol unit, 1,3-butanediol unit, 1,4-butanediol unit, 1,6-hexanediol unit, neopentyl glycol unit, 1,2-ethylhexyl diol unit, 1,5-pentanediol unit, 1,10-decanediol unit, 1,3-cyclohexanedimethanol unit, 1,4-cyclohexanedimethanol unit, glycerin unit, and trimethylolpropane unit.

[0122] In Chemical Formula 5, n is an arbitrary number, and its range may be selected in consideration of the desired physical properties, and for example, it may be about 2 to 10 or 2 to 5.

[0123] In Chemical Formula 6, m is an arbitrary number, and its range may be selected in consideration of the desired physical properties, and for example, it may be about 1 to 10 or 1 to 5.

[0124] The polyol according to an example of the present application may be the polyol represented by the following Chemical Formula 7.

[0125]

Chemical Formula

[0126] In Chemical Formula 7, L 10 may be a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 2 to 20 carbon atoms, or a linear or branched alkynylene group having 2 to 20 carbon atoms.

[0127] Said L 10 The linear or branched alkylene group may each independently have 1 or more or 2 or more carbon atoms, and may have 10 or less, 8 or less, 6 or less, or 4 or less carbon atoms. Also, said L 10 The linear or branched alkenylene group or linear or branched alkynylene group may each independently have 2 or more or 3 or more carbon atoms, and may have 10 or less, 8 or less, 6 or less, or 4 or less carbon atoms.

[0128] Also, in Chemical Formula 7, n may be a number of 1 or more, 3 or more, 5 or more, or 7 or more, and in other examples, may be a number of 20 or less, 16 or less, 12 or less, or 8 or less.

[0129] The main component part of the two-component curable composition according to an example of the present application may contain a filler as required in the process.

[0130] In order to obtain excellent heat dissipation performance, it is conceivable that a filler is used in a high content in the main component part of the present application. In the main component part of the present application, the content of the filler may be 80% by weight or more, 82.5% by weight or more, 85% by weight or more, or 87.5% by weight or more based on the total weight of the main component part, and in other examples, the content of the filler may be 95% by weight or less, 92.5% by weight or less, or 90% by weight or less based on the total weight of the main component part. Here, the content of the filler may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0131] Here, the filler has the same content as the filler contained in the curable composition according to an example of the present application, and detailed content is omitted.

[0132] The main component part according to the present application may further contain an additive, and the additive has the same content as the additive contained in the curable composition according to an example of the present application, and detailed content is omitted. Further, the additive may be further contained in a state where the main component part with or without the additive and the curing agent part with or without the additive are mixed.

[0133] In the two-component curable composition according to an example of the present application, the main component part may be contained in an amount of 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, or 90 parts by weight or more with respect to 100 parts by weight of the curing agent part. In another example, the main component part may be contained in an amount of 200 parts by weight or less, 180 parts by weight or less, 160 parts by weight or less, 140 parts by weight or less, or 120 parts by weight or less with respect to 100 parts by weight of the curing agent part. Here, the content of the main component part in the two-component curable composition may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0134] Further, at least one of the main component part and the curing agent part of the two-component curable composition according to an example of the present application contains a filler, and the total content of the filler contained in the two-component curable composition may be 80% by weight or more, 82.5% by weight or more, 85% by weight or more, or 87.5% by weight or more with respect to the total weight of the two-component curable composition. In another example, the total content of the filler may be 95% by weight or less, 92.5% by weight or less, or 90% by weight or less with respect to the total weight of the two-component curable composition. Here, the content of the filler may be within a range formed by appropriately selecting the above-listed upper and lower limits.

[0135] The two-component curable composition can be cured to form a cured product, and may have at least one or more of the following physical properties. Each of the following physical properties is independent, and any one physical property does not take precedence over other physical properties. The cured product of the two-component curable composition can satisfy at least one or two or more of the following physical properties. The cured product of the two-component curable composition that satisfies at least one or two or more of the following physical properties is due to the combination of each component.

[0136] The two-component curable composition can have a thermal conductivity of about 2.5 W / m·K or more when measured according to ASTM D5470 standard or ISO 22007-2 standard along the thickness direction of a sample (cured product) with a thickness of 4 mm. In other examples, the thermal conductivity may be about 2.6 W / m·K or more, about 2.7 W / m·K or more, about 2.8 W / m·K or more, about 2.9 W / m·K or more, or about 3.0 W / m·K or more. Since a higher numerical value of the thermal conductivity means higher thermal conductivity, its upper limit is not particularly limited. For example, the thermal conductivity may be 20 W / m·K or less, 18 W / m·K or less, 16 W / m·K or less, 14 W / m·K or less, 12 W / m·K or less, 10 W / m·K or less, 8 W / m·K or less, 6 W / m·K or less, or 4 W / m·K or less.

[0137] The cured product of the two-component curable composition may have a thermal resistance of about 5 K / W or less, about 4.5 K / W or less, about 4 K / W or less, about 3.5 K / W or less, about 3 K / W or less, or about 2.8 K / W or less. When adjusting to obtain a thermal resistance within such a range, excellent cooling efficiency or heat dissipation efficiency can be ensured. The thermal resistance may be a value measured according to ASTM D5470 standard or ISO 22007-2 standard, and the measurement method is not particularly limited.

[0138] The cured product of the two-component curable composition may have appropriate adhesive strength with respect to any substrate or module case with which the cured product of the two-component curable composition is in contact. If appropriate adhesive strength can be ensured, peeling due to volume change during charge and discharge, change in the operating temperature of the battery module, or curing shrinkage, etc. can be prevented with respect to various materials, for example, the case or battery cells included in the battery module, and excellent durability can be ensured. Further, re-workability that enables separation and reattachment of the module during the assembly process of the battery pack can be ensured.

[0139] The cured product of the two-component curable composition can ensure durability for application to products that require a long warranty period such as automobiles (in the case of automobiles, about 15 years or more). Durability means that after holding at a low temperature of about -40°C for 30 minutes and then raising the temperature to 80°C again and holding for 30 minutes as one cycle, after repeating the cycle 100 times in a thermal shock test, it does not separate from or peel off the module case or battery cells of the battery module, or cracks do not occur.

[0140] The cured product of the two-component curable composition may have an electrical insulation of 10 kV / mm or more, 15 kV / mm or more, or 20 kV / mm or more. The breakdown voltage may be about 50 kV / mm or less, 45 kV / mm or less, 40 kV / mm or less, 35 kV / mm or less, 30 kV / mm or less, although the higher the value, the better the electrical insulation of the cured product of the two-component curable composition, and it is not particularly limited. To achieve the breakdown voltage as described above, an insulating filler may be applied to the two-component curable composition. Generally, among thermal conductive fillers, ceramic fillers are known as components that can ensure insulation. The electrical insulation can be measured by the breakdown voltage measured according to ASTM D149 standard. Further, if the cured product of the two-component curable composition can ensure the electrical insulation as described above, performance can be maintained and stability can be ensured with respect to various materials, for example, the case or battery cells included in the battery module.

[0141] The cured product of the two-component curable composition has a volume resistivity of 1×10 10 Ω·cm or more, 3×10 10 Ω·cm or more, 7×10 10 Ω·cm or more, or 9×10 10 Ω·cm or more. In other examples, the cured product of the two-component curable composition may have a volume resistivity of 1×10 14 Ω·cm or less, 7.5×10 13 Ω·cm or less, 5×10 13 Ω·cm or less, 2.5×10 13 Ω·cm or less, or 1×10 13 Ω·cm or less. Here, the volume resistivity of the cured product of the two-component curable composition may be within a range formed by appropriately selecting the above-listed upper and lower limits. The volume resistivity can be measured using a volume resistivity measuring device with a cured product of the two-component curable composition having a thickness of 0.2 cm according to the ASTM D257 standard. If the cured product of the two-component curable composition can ensure the above-mentioned volume resistivity, excellent electrical insulation performance can be ensured, so it can be used in various materials, such as cases or battery cells included in battery modules, to maintain performance and ensure stability.

[0142] The cured product of the two-component curable composition may have a specific gravity of 5 or less. In other examples, the specific gravity may be 4.5 or less, 4 or less, 3.5 or less, or 3 or less. Since the lower the numerical value of the specific gravity of the cured product of the two-component curable composition, the more advantageous it is for weight reduction of the applied product, the lower limit is not particularly limited. For example, the specific gravity may be about 1.5 or more or 2 or more. In order for the cured product of the two-component curable composition to exhibit a specific gravity within the above range, for example, when adding a thermal conductivity filler, a filler that can ensure the desired thermal conductivity even at a relatively low specific gravity, that is, a filler with a low specific gravity itself, or a method of applying a filler subjected to surface treatment may be used.

[0143] It is appropriate that the cured product of the two-component curable composition contains as few volatile substances as possible. For example, the cured product of the two-component curable composition may have a proportion of non-volatile components of 90% by weight or more, 95% by weight or more, or 98% by weight or more. The ratio with the non-volatile component can be defined by the following method. That is, the non-volatile component can be defined as the portion remaining after maintaining the cured product of the two-component curable composition at 100 ° C for about 1 hour, and therefore the ratio can be measured based on the ratio of the initial weight of the cured product of the two-component curable composition to the weight of the portion remaining after holding at 100 ° C for about 1 hour.

[0144] The cured product of the two-component curable composition may have excellent resistance to deterioration as required, and may be required to have stability that does not chemically react as much as possible.

[0145] It can be advantageous for the cured product of the two-component curable composition to have a low shrinkage rate during or after curing. Thereby, it is possible to prevent the occurrence of peeling or voids that may occur during the production or use of various materials, such as the cases or battery cells included in the battery module. The shrinkage rate may be appropriately adjusted within a range that can exhibit the above-described effects. For example, it may be less than 5%, less than 3%, or about less than 1%. Since the lower the shrinkage rate value, the more advantageous it is, the lower limit is not particularly limited.

[0146] It can be advantageous for the cured product of the two-component curable composition to have an even lower coefficient of thermal expansion (CTE). Thereby, it is possible to prevent the occurrence of peeling or voids that may occur during the production or use of various materials, such as the cases or battery cells included in the battery module. The coefficient of thermal expansion may be appropriately adjusted within a range that exhibits the above-described effects. For example, it may be less than 300 ppm / K, less than 250 ppm / K, less than 200 ppm / K, less than 150 ppm / K, or less than 100 ppm / K. Since the lower the coefficient of thermal expansion value, the more advantageous it is, the lower limit is not particularly limited.

[0147] The cured product of the two-component curable composition may have its tensile strength appropriately adjusted, thereby ensuring excellent impact resistance and the like. The tensile strength may be adjusted, for example, in the range of about 1.0 MPa or more.

[0148] The cured product of the two-component curable composition may further have a 5% weight loss temperature in thermogravimetric analysis (TGA) of 400 °C or higher, or an 800 °C residue amount of 70% by weight or more. Such characteristics can further improve the high-temperature stability for various materials, such as cases or battery cells included in battery modules. In other examples, the 800 °C residue amount may be about 75% by weight or more, about 80% by weight or more, about 85% by weight or more, or about 90% by weight or more. In other examples, the 800 °C residue amount may be about 99% by weight or less. The thermogravimetric analysis (TGA) may be measured in the range of 25 °C to 800 °C at a heating rate of 20 °C / min under a nitrogen (N2) atmosphere of 60 cm 3 / min. The thermogravimetric analysis (TGA) results can also be achieved through the adjustment of the composition of the cured product of the two-component curable composition. For example, the 800 °C residue amount depends on the type or proportion of the thermally conductive filler contained in the cured product of the two-component curable composition. If an excessive amount of the thermally conductive filler is included, the residue amount will increase. However, when the polymer and / or monomer used in the two-component curable composition has generally higher heat resistance than other polymers and / or monomers, the residue amount will be even higher. Thus, the polymer and / or monomer components contained in the cured product of the two-component curable composition also affect its hardness.

[0149] Of course, the two-component curable composition of the present application, and the curable composition according to an example of the present application, may be formed by mixing the above-listed components. Also, for the two-component curable composition of the present application and the curable composition according to an example of the present application, as long as all the necessary components are included, there is no particular limitation on the mixing order.

[0150] The two-component curable composition using the curable composition of the present application can dissipate heat generated when used in various electrical products and electronic products such as irons, washing machines, dryers, clothing management machines, electric shavers, microwave ovens, electric ovens, electric rice cookers, refrigerators, dishwashers, air conditioners, fans, humidifiers, air purifiers, mobile phones, radios, TVs, radios, computers, laptops, or batteries such as secondary batteries. In particular, in a battery electric vehicle battery manufactured by gathering battery cells to form one battery module and gathering a plurality of battery modules to form one battery pack, a curable composition according to an example of the present application may be used as a material for connecting the battery modules. When a curable composition according to an example of the present application is used as a material for connecting battery modules, it can dissipate heat generated from the battery cells and play a role in fixing the battery cells from external shocks and vibrations.

[0151] The cured product of the two-component curable composition of the present application can transfer heat generated from the heat-generating element to the cooling part. That is, the cured product of the two-component curable composition can dissipate heat generated from the heat-generating element.

[0152] The cured product of the two-component curable composition is located between the heat-generating element and the cooling part and can bring them into thermal contact. Thermal contact means that the cured product of the two-component curable composition physically and directly contacts the heat-generating element and the cooling part to dissipate the heat generated from the heat-generating element to the cooling part, or even if the cured product of the two-component curable composition does not directly contact the heat-generating element and / or the cooling part (that is, there is a separate layer between the cured product of the curable composition and the heat-generating element and / or the cooling part), it means dissipating the heat generated from the heat-generating element to the cooling part.

Advantages of the Invention

[0153] The present application can provide a curable composition with little viscosity change over time, excellent compatibility with fillers, and ensured processability.

[0154] This application can provide a curable composition capable of forming a cured product having excellent electrical insulation performance.

[0155] This application can provide an apparatus including a cured product of a curable composition that thermally contacts a heating element and a cooling part.

Mode for Carrying Out the Invention

[0156] Hereinafter, the present invention will be described through Examples and Comparative Examples, but the scope of the present invention is not limited by the following content.

[0157] Substances Used (1) Isocyanate Compound As the polyfunctional isocyanate compound, a hexamethylene diisocyanate trimer (GPC-measured weight average molecular weight: 827 g / mol, PDI: 1.167), which is a trifunctional isocyanate compound, was used.

[0158] In addition, as the bifunctional isocyanate compound, hexamethylene diisocyanate (GPC-measured weight average molecular weight: 174 g / mol, PDI: 1.018), isophorone diisocyanate (GPC-measured weight average molecular weight: 232 g / mol, PDI: 1.041), or dicyclohexylmethane diisocyanate (GPC-measured weight average molecular weight: 233 g / mol, PDI: 1.036) was used.

[0159] (2) Production Example of Polyol and Main Agent Part The main agent part included in the two-component curable composition according to an example of this application contains a polyol and may further contain a filler and / or an additive as necessary.

[0160] As the polyol contained in the main agent part, a caprolactone-based polyol having a weight average molecular weight of 860 g / mol was used.

[0161] The main component part (P) contained in the two-component curable composition is produced by adding the polyol (P1), filler (P2), and additive (P3) in a weight ratio of 5:50:1.155 (P1:P2:P3), and stirring the added substances in a paste mixer at 600 rpm in the revolution direction and 500 rpm in the rotation direction.

[0162] The filler (P2) contains spherical alumina (aluminum oxide) with an average particle size of about 80 μm, etc., and other additives (P3) such as plasticizers and flame retardants are used.

[0163] Example 1 Hexamethylene diisocyanate trimer (R11) and hexamethylene diisocyanate (R12) were mixed in a weight ratio of 6:4 (R11:R12) to produce an isocyanate mixture (R1) which is a resin component.

[0164] The isocyanate mixture (R1), filler (R2), and other additives (R3) were added in a weight ratio of 5:50:2 (R1:R2:R3), and the added substances were uniformly mixed in a paste mixer to produce the curable composition (R) according to the present application.

[0165] Here, the filler (R2) contains spherical alumina (aluminum oxide) with an average particle size of about 80 μm, etc., and other additives (R3) such as plasticizers and flame retardants are used.

[0166] Also, the curable composition (R) and the main component part (P) according to the production example of the main component part were mixed in a weight ratio of 1:1 (R:P) to produce a two-component curable composition (U).

[0167] Example 2 A curable composition (R) and a two-component curable composition (U) were produced in the same manner as in Example 1, except that a hexamethylene diisocyanate trimer (R11) and hexamethylene diisocyanate (R12) were mixed at a weight ratio of 7:3 (R11:R12) to produce an isocyanate mixture (R1) as a resin component.

[0168] Example 3 A curable composition (R) and a two-component curable composition (U) were produced in the same manner as in Example 1, except that a hexamethylene diisocyanate trimer (R11) and hexamethylene diisocyanate (R12) were mixed at a weight ratio of 8:2 (R11:R12) to produce an isocyanate mixture (R1) as a resin component.

[0169] Example 4 A curable composition (R) and a two-component curable composition (U) were produced in the same manner as in Example 1, except that a hexamethylene diisocyanate trimer (R11) and isophorone diisocyanate (R13) were mixed at a weight ratio of 6:4 (R11:R13) to produce an isocyanate mixture (R1) as a resin component.

[0170] Example 5 A curable composition (R) and a two-component curable composition (U) were produced in the same manner as in Example 1, except that a hexamethylene diisocyanate trimer (R11) and isophorone diisocyanate (R13) were mixed at a weight ratio of 7:3 (R11:R13) to produce an isocyanate mixture (R1) as a resin component.

[0171] Example 6 A curable composition (R) and a two-component curable composition (U) were produced in the same manner as in Example 1, except that a hexamethylene diisocyanate trimer (R11) and isophorone diisocyanate (R13) were mixed at a weight ratio of 8:2 (R11:R13) to produce an isocyanate mixture (R1) as a resin component.

[0172] Example 7 A curable composition (R) and a two-component curable composition (U) were produced in the same manner as in Example 1, except that a hexamethylene diisocyanate trimer (R11) and dicyclohexylmethane diisocyanate (R14) were mixed at a weight ratio of 6:4 (R11:R14) to produce an isocyanate mixture (R1) as a resin component.

[0173] Example 8 A curable composition (R) and a two-component curable composition (U) were produced in the same manner as in Example 1, except that a hexamethylene diisocyanate trimer (R11) and dicyclohexylmethane diisocyanate (R14) were mixed at a weight ratio of 7:3 (R11:R14) to produce an isocyanate mixture (R1) as a resin component.

[0174] Example 9 A curable composition (R) and a two-component curable composition (U) were produced in the same manner as in Example 1, except that a hexamethylene diisocyanate trimer (R11) and dicyclohexylmethane diisocyanate (R14) were mixed at a weight ratio of 8:2 (R11:R14) to produce an isocyanate mixture (R1) as a resin component.

[0175] Comparative Example 1 A two-component curable composition (U) was produced in the same manner as in Example 1, except that a hexamethylene diisocyanate trimer (R11), a filler (R2), and other additives (R3) were added at a weight ratio of 5:50:2 (R1:R2:R3), and the added substances were uniformly mixed with a paste mixer to produce a curable composition (R) according to the present application.

[0176] <Physical Property Measurement Method> (1) Method for Measuring Volume Resistance of Cured Product of Two-Component Curable Composition The volume resistance of the cured product of the two-component curable composition (U) was measured according to the ASTM D257 measurement standard.

[0177] The two-component curable composition (U) was left to stand at room temperature and normal humidity (about 30 - 70% RH) for 24 hours to produce a cured product of the two-component curable composition in the form of a disk with a diameter of 10 cm and a thickness of about 0.2 cm.

[0178] A voltage of 500 V, a measurement time of 1 minute, and the thickness of the cured product of the two-component curable composition were input into a volume resistivity measuring device (HIRESTA-US MCP-HT800, supplier: Mitsubishi Chemical Corporation), and the volume resistivity of the cured product of the two-component curable composition was measured.

[0179] (2) Method for evaluating the compatibility of the curable composition The compatibility of the curable composition (R) was visually distinguished according to the following criteria under normal temperature and normal humidity conditions.

[0180] The compatibility of the curable composition (R) directly affects the compatibility of the two-component curable composition (U). That is, when the compatibility of the curable composition (R) is poor, the compatibility of the two-component curable composition (U) tends to be poor, and when the compatibility of the curable composition (R) is excellent, the compatibility of the two-component curable composition (U) tends to be excellent.

[0181] Therefore, the compatibility of the two-component curable composition (U) can be predicted in the evaluation of the compatibility of the curable composition (R) as follows.

[0182] ○○: When the curable composition immediately after mixing is uniformly mixed ○: When the curable composition immediately after mixing is uniformly mixed, but has slightly lower fluidity compared to ○○ △: When the filler in the curable composition immediately after mixing solidifies and is not uniformly mixed, but becomes uniformly mixed after further adding a dispersant ×: When the filler settles in the curable composition immediately after mixing, or when the filler in the curable composition immediately after mixing solidifies and is not uniformly mixed, and becomes uniformly mixed after further adding a dispersant, but has slightly lower fluidity compared to △

[0183] (3) Method for Measuring Viscosity Change Rate of Curable Composition after 12 Days The viscosity change rate of the curable composition (R) after 12 days was measured by the following formula 3. Here, 1 day means 24 hours, and the viscosity after 12 days means the viscosity after 288 hours.

[0184] [Formula 3] Viscosity change rate after 12 days = μ f / μ i

[0185] The above μ f is the viscosity measured after leaving the curable composition at room temperature for 12 days, The above μ i is the viscosity of the curable composition before leaving it at room temperature for 12 days (initial room temperature viscosity).

[0186] At this time, μ i and μ f are the respective values measured after rotating for 180 seconds at a shear rate of 2.4 / s using a viscometer (manufacturer: Brookfield, model name: DV3THB-CP) and a spindle CPA-52Z.

[0187] (4) Method for Measuring Viscosity of Resin Component The viscosity of the resin component was measured using a viscometer (manufacturer: Brookfield, model name: Brookfield LV) and a spindle LV-63. After adjusting the zero point of the viscometer, the spindle LV-63 was attached to the spindle connection part of the viscometer.

[0188] A plate was attached to the plate connection part of the viscometer, and it was adjusted through an adjustment lever so that a certain separation space (gap) was formed between the spindle and the plate. The plate was separated, and about 0.5 mL of the resin component was applied to the center of the separated plate. The plate coated with the resin component was attached again to the plate connection part of the viscometer, and after waiting until the torque value became 0, the measurement was carried out.

[0189] The viscosity used was the viscosity value measured at a rotational speed of 20 rpm or 100 rpm as the viscosity of the resin component.

[0190] (5) Method for measuring the number-average molecular weight and weight-average molecular weight of the resin component The number-average molecular weight (M n ) and weight-average molecular weight (M w ) of the resin component (R1) were measured using GPC (gel permeation chromatography). The resin component to be analyzed was placed in a 20 mL vial and diluted with a THF (tetrahydrofuran) solvent to a concentration of approximately 20 mg / mL. Then, the calibration standard sample and the sample to be analyzed were filtered through a syringe filter (pore size: 0.2 μm) and then measured. The analysis program used ChemStation from Agilent technologies. The elution time of the sample was compared with the calibration curve to determine the number-average molecular weight (M n ) and weight-average molecular weight (M w ). Here, the polydispersity index (PDI) was the value obtained by dividing the weight-average molecular weight (M w ) by the number-average molecular weight (M n ).

[0191] <GPC measurement conditions> Equipment: 1200 series from Agilent technologies Column: TL Mix.A&B from Agilent technologies was used Solvent: THF Column temperature: 40 °C Sample concentration: 20 mg / mL, 10 μL injection MP: 364000, 91450, 17970, 4910, 1300 were used as standard samples

[0192] (6) Method for measuring the thermal conductivity of the cured product of the two-component curable composition The thermal conductivity was measured using the Hot disk method. Specifically, the thermal conductivity was measured with a thermal constant analyzer in accordance with ISO 22007-2 standard along the thickness direction of each of the final two-component curable compositions produced in the above Examples and Comparative Examples, in a state where the compositions were cured into disk-shaped samples with a diameter of 2 cm and a thickness of 4 mm.

[0193] <Physical property measurement results> The physical properties of the above Examples and Comparative Examples were measured, and the results are as shown in Table 1 below.

[0194]

Table 1

[0195] Referring to Table 1, Examples 1 to 9 had good compatibility and little viscosity change over time. Also, it can be seen that the cured products according to Examples 1 to 9 also had excellent electrical insulation performance and thermal conductivity.

[0196] On the other hand, in Comparative Example 1, although the cured product had excellent electrical insulation performance, it had poor compatibility and a large viscosity change over time.

Claims

1. A curable composition comprising a resin component containing a polyfunctional isocyanate compound and a bifunctional isocyanate compound, and a filler.

2. The curable composition according to claim 1, wherein the resin component has a weight average molecular weight in the range of 400 to 1,000 g / mol.

3. The curable composition according to claim 1 or 2, wherein the resin component has a polydispersity index (PDI) in the range of 1.2 to 1.

8.

4. The curable composition according to any one of claims 1 to 3, wherein the polyfunctional isocyanate compound has a weight average molecular weight of 600 to 2,000 g / mol and a polydispersity index (PDI) in the range of 0.8 to 1.

5.

5. The curable composition according to any one of claims 1 to 4, wherein the bifunctional isocyanate compound has a weight average molecular weight of 100 to 500 g / mol and a polydispersity index (PDI) in the range of 0.8 to 1.

4.

6. The curable composition according to any one of claims 1 to 5, wherein the resin component has a K value of 0.4 or more according to the following formula 1. [Formula 1] K = Σ(N × W) In formula 1, N is a value obtained by the following formula 2 for each isocyanate compound contained in the resin component, and W is the content (weight %) of the each isocyanate compound based on the total amount of the isocyanate compounds contained in the resin component. [Formula 2] N = F / M In formula 2, F is the number of isocyanate groups of the each isocyanate compound, and M is the weight average molecular weight (g / mol) of the each isocyanate compound.

7. The curable composition according to any one of claims 1 to 6, wherein the resin component has a normal temperature viscosity in the range of 400 to 600 cP.

8. The curable composition according to any one of claims 1 to 7, wherein the resin component contains 15 to 80 parts by weight of the bifunctional isocyanate compound with respect to 100 parts by weight of the polyfunctional isocyanate compound.

9. The curable composition according to any one of claims 1 to 8, containing 80 to 95% by weight of the filler.

10. A two-component curable composition comprising a main agent part containing a resin component containing a polyol, and a curing agent part containing the curable composition according to any one of claims 1 to 9.

11. Volume resistance is 1 x 10 １０ ~1×10 １４ The two-part curable composition according to claim 10, which forms a cured product having a viscosity in the range of Ω·cm.

12. Including a heat generating element and a cooling part, An apparatus comprising a cured product of the two-component curable composition according to claim 10 or 11, in which the heat-generating element and the cooling part are in thermal contact with each other.

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