Hardening composition

Abstract

The present invention provides a curable composition, a thermal interface material (TIM), and uses thereof. In the present invention, the curable composition or the thermal interface material, etc., can exhibit a low adhesive force with respect to a predetermined adherend while showing a high thermal conductivity. Further, in the present invention, the low adhesive force can be achieved without using an adhesion regulating component such as a plasticizer or while minimizing the usage ratio thereof. In the present invention, further, the curable composition can exhibit a precisely controlled curing rate and at the same time can have excellent curability. In the present invention, further, a product containing the curable composition, a cured product thereof, or a thermal interface material can be provided.

Description

Technical Field

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0116477 filed on September 15, 2022, and all contents disclosed in the document of the Korean Patent Application are incorporated herein by reference.

[0002] The present invention relates to a curable composition, a thermal interface material (TIM), and uses thereof.

Background Art

[0003] With the increase in electrical or electronic devices that require heat management, such as batteries, the importance of heat dissipation materials such as TIM (Thermal Interface Material) has been increasing. Various types of heat dissipation materials are known. As one of the conventional heat dissipation materials, a material in which a heat conductive filler is filled in a resin binder is known (for example, Patent Document 1).

[0004] In the heat dissipation materials as described above, as the resin binder, usually, a silicone resin, a polyolefin resin, an acrylic resin, an epoxy resin, or the like is used.

[0005] Basically, a heat dissipation material is required to have excellent thermal conductivity, and further functions are also required depending on the application. For example, depending on the application, it is required that the heat dissipation material exhibits low adhesive strength to a specific adherend together with high thermal conductivity.

[0006] For example, when it is necessary to replace a component in contact with the heat dissipation material in a product or when it is necessary to change the position of the heat dissipation material or the like during the process, the heat dissipation material needs to exhibit low adhesive strength.

[0007] Among well-known heat dissipation materials, there is a material that exhibits low adhesive strength, which is a material using silicone resin as a resin binder. However, silicone resin is relatively expensive. In addition, silicone resin contains components that cause poor contact when applied to electronic / electrical products, so its applications are limited.

[0008] The polyurethane material also applied in Patent Document 1 can form a heat dissipation material having high thermal conductivity and has various other advantages, but it is a material that exhibits high adhesive strength to many adherends.

[0009] As a method for reducing the adhesive strength of a material that exhibits high adhesive strength, there is a method of blending a component known as a so-called plasticizer. However, a large amount of plasticizer blended for controlling the adhesive strength has problems such as damaging the inherent advantages of the material itself or eluting during the use process.

[0010] In addition, for a heat dissipation material having curability, it is necessary to control the curing rate of the heat dissipation material.

[0011] That is, when forming a heat dissipation material using a heat dissipation material having curability, after applying the heat dissipation material before curing to the target position, a step of curing it is performed. By the way, even after applying the heat dissipation material, it may be necessary to replace parts in the product that come into contact with the heat dissipation material, or to change the position of the heat dissipation material and / or the said parts. However, when the curing of the heat dissipation material occurs rapidly, the viscosity and hardness of the said material also increase rapidly, so there is a problem that the time during which the said replacement or position change is possible becomes very short.

[0012] In addition, when the curing of the heat dissipation material occurs rapidly, the time during which the material can be applied using a dispenser device or an injection device also becomes short. Usually, in the step of applying the heat dissipation material, there may be a waiting time after loading the heat dissipation material into the dispenser device or the injection device. However, when the curing of the heat dissipation material occurs rapidly, it is not possible to appropriately ensure the said waiting time.

Prior Art Documents

Patent Document

[0013]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0014] The present invention aims to provide a curable composition, a thermal interface material (TIM), and their uses. The thermal interface material may be formed by curing the curable composition. One object of the present invention is to make the curable composition or thermal interface material show a high thermal conductivity while showing a low adhesive force to a predetermined adherend. Also included in the object of the present invention is to achieve the low adhesive force without using an adhesion adjusting component such as a plasticizer or minimizing its usage ratio.

[0015] The present invention also aims to make the curable composition show a precisely controlled curing rate while having excellent curability.

[0016] The present invention also aims to provide a product containing the curable composition, its cured body, or the thermal interface material.

Means for Solving the Problems

[0017] Among the physical properties mentioned in this specification, when the measurement temperature affects the result, unless otherwise specified, the physical property is the physical property measured at room temperature. The term "room temperature" is the natural temperature without heating and cooling, and usually means any temperature within the range of about 10°C to 30°C or a temperature of about 23°C or about 25°C. Also, unless otherwise specified in this specification, the unit of temperature is °C.

[0018] Among the physical properties mentioned in this specification, when the measurement pressure affects the results, unless otherwise specified, the physical property is the one measured at normal pressure. The term "normal pressure" refers to the natural pressure without pressurization or depressurization, and usually, the atmospheric pressure within the range of about 700 mmHg to 800 mmHg is referred to as normal pressure.

[0019] The present invention relates to a resin composition. The term "resin composition" means a composition containing components known as resins in the industry or a composition that does not contain resins but contains components capable of forming resins through a curing reaction or the like. Therefore, in this specification, the scope of the term "resin or resin component" includes not only components generally known as resins but also components capable of forming resins through curing and / or polymerization reactions.

[0020] The resin composition may be a curable composition. The curable composition can be cured to form a thermal interface material (TIM: Thermal Interface Material). Therefore, in this specification, the cured product of the resin composition and the thermal interface material can refer to the same object.

[0021] When the resin composition of the present invention is a curable composition, the resin composition may be a one-component type or a two-component type composition. The term "one-component type composition" means a resin composition in which the components participating in curing are contained in a state where they are physically in contact with each other, and the term "two-component type composition" means a resin composition in which at least a part of the components participating in curing are physically separated and contained separately.

[0022] When the resin composition of the present invention is a curable composition, the resin composition may be a room temperature curable type, a heat curable type, an energy ray curable type and / or a moisture curable type. The term "room temperature curable type" refers to a resin composition in which the curing reaction can be started and / or proceed at room temperature. The term "heat curable type" refers to a resin composition in which the curing reaction can be started and / or proceed by applying heat. The term "energy ray curable type" refers to a resin composition in which the curing reaction can be started and / or proceed by irradiation with energy rays (for example, ultraviolet rays, electron beams, etc.). The term "moisture curable type" refers to a resin composition in which the curing reaction can be started and / or proceed in the presence of moisture.

[0023] The resin composition of the present invention may be a solvent type or a solventless type. Considering the viewpoints of application efficiency and environmental load, etc., it is appropriate that it is a solventless type.

[0024] The resin composition of the present invention may be a polyurethane composition. In such a case, the resin composition may contain polyurethane or may contain components capable of forming polyurethane. For example, the heat interface material which is a cured product of the resin composition may contain the polyurethane. The polyurethane can be formed by the reaction of a curable component and its curing agent described later in one example.

[0025] The resin composition of the present invention can exhibit a low adhesive force to a specific adherend or can form a cured product that can exhibit a low adhesive force. Such a resin composition may be the polyurethane composition. Polyurethane is known as an adhesive material that can exhibit excellent adhesiveness to various adherends. Therefore, as a method for the polyurethane composition to exhibit a low adhesive force to an adherend, usually, a method of introducing a component that reduces the adhesive force, such as a plasticizer, is used. When such a component such as a plasticizer is applied, the adhesive force of the polyurethane material can be reduced, but problems may occur such as reducing other physical properties that the component could ensure in the polyurethane or eluting the component outside the material during the use process of the polyurethane material. However, in the present invention, it is possible to achieve the low adhesive force with respect to the polyurethane material without using an adhesive force-reducing component such as a plasticizer or while minimizing its usage amount. Therefore, in the present invention, it is possible to provide a material that solves the problem of high adhesive force not required according to the application while taking advantage of the polyurethane material.

[0026] The adhesive force of the resin composition or its cured product to aluminum may be 1 N / mm 2 or less. The upper limit of the adhesive force of the resin composition or its cured product to aluminum may be 0.9 N / mm, 2 0.8 N / mm, 2 0.7 N / mm, 2 0.6 N / mm, 2 0.5 N / mm, 2 0.4 N / mm, 2 0.3 N / mm, 2 0.2 N / mm, 2 0.1 N / mm, 2 0.15 N / mm, 2 0.09 N / mm, 2 0.08 N / mm, 2 0.07 N / mm, 2 0.06 N / mm, 2 0.04 N / mm, 2 or 0.03 N / mm 2It may be. The adhesive force of the resin composition or its cured product to aluminum may be equal to or less than any one of the above-mentioned upper limits. In the present invention, the lower limit of the adhesive force to aluminum is not particularly limited. In one example, the adhesive force to aluminum is 0 N / mm 2 or more or 0 N / mm 2 exceeding. The resin composition may be a resin composition in which the adhesive force to aluminum is substantially not measured, or a resin composition capable of forming a cured product in which the adhesive force is substantially not measured. Therefore, the adhesive force to aluminum is 0 N / mm 2 or more or 0 N / mm 2 exceeding and equal to or less than any one of the above-mentioned upper limits. The adhesive force of the resin composition or its cured product to aluminum can be measured by the method described in the examples of this specification.

[0027] The resin composition or its cured product may have an adhesive strength to polyester of 100 gf / cm or less. In other examples, the upper limit of the adhesive strength of the resin composition or its cured product to polyester may be 95 gf / cm, 90 gf / cm, 85 gf / cm, 80 gf / cm, 75 gf / cm, 70 gf / cm, 65 gf / cm, 60 gf / cm, 55 gf / cm, 50 gf / cm, 45 gf / cm, 40 gf / cm, 35 gf / cm, 30 gf / cm, 25 gf / cm, or 20 gf / cm. The adhesive strength of the resin composition or its cured product to polyester may be equal to or less than any one of the upper limits described above. In the present invention, the lower limit of the adhesive strength to polyester is not particularly limited. In one example, the lower limit of the adhesive strength of the resin composition or its cured product to polyester may be about 0 gf / cm, 2 gf / cm, 4 gf / cm, 6 gf / cm, 8 gf / cm, 10 gf / cm, 12 gf / cm, 14 gf / cm, 16 gf / cm, 18 gf / cm, 20 gf / cm, 25 gf / cm, 30 gf / cm, 35 gf / cm, 40 gf / cm, 45 gf / cm, 50 gf / cm, 55 gf / cm, or 60 gf / cm. The resin composition or its cured product may not substantially exhibit an adhesive strength to polyester. The adhesive strength of the resin composition or its cured product to polyester may be in the range between any one of the lower limits described above and any one of the upper limits described above. The adhesive strength of the resin composition or its cured product to polyester can be measured by the method described in the examples of this specification.

[0028] The resin composition or its cured product can exhibit excellent thermal conductivity characteristics. For example, the lower limit of the thermal conductivity of the resin composition or its cured product may be about 1.2 W / mK, 1.4 W / mK, 1.6 W / mK, 1.8 W / mK, 2.0 W / mK, 2.2 W / mK, 2.4 W / mK, or 2.6 W / mK. The thermal conductivity may be equal to or higher than any one of the lower limits described above. There is no special limitation on the upper limit of the thermal conductivity. For example, the resin composition or its cured product may have an upper limit of thermal conductivity of about 10 W / mK, 9 W / mK, 8 W / mK, 7 W / mK, 6 W / mK, 5 W / mK, 4 W / mK, or 3 W / mK. The thermal conductivity may be in the range between any one of the lower limits described above and any one of the upper limits described above. The thermal conductivity of such a resin composition or its cured product can be measured by the method disclosed in the examples described below.

[0029] The resin composition or its cured product can also exhibit appropriate hardness. For example, if the hardness of the resin composition or its cured product is too high, it may become significantly brittle and problems may occur. Also, by adjusting the hardness of the resin composition or its cured product, impact resistance and vibration resistance can be ensured according to the intended application, and the durability of the product can be ensured. The upper limit of the shore OO type hardness of the resin composition or its cured product may be 150, 140, 130, 120, 110, 100, 90, or 85. The shore OO type hardness may be equal to or lower than any one of the upper limits described above. The lower limit of the shore OO type hardness may be 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85. The shore OO type hardness may be equal to or higher than any one of the lower limits described above. The shore OO type hardness may be within the range between any one of the upper limits described above and any one of the lower limits described above. The hardness of such a resin composition or its cured product can be measured by the method disclosed in the examples described below.

[0030] The resin composition or its cured product can also exhibit appropriate flexibility. For example, by adjusting the flexibility of the resin composition or its cured product to a desired level, the applicable uses can be greatly expanded. For example, the upper limit of the bending radius of the resin composition or its cured product may be about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9 or 8. The bending radius may be equal to or less than any one of the above-mentioned upper limits. The lower limit of the bending radius may be, for example, about 1, 2, 3, 4, 5, 6, 7, 8 or 9. The bending radius may be equal to or greater than any one of the above-mentioned lower limits. The bending radius may be within the range between any one of the above-mentioned upper limits and any one of the above-mentioned lower limits. The bending radius of such a resin composition or its cured product can be measured by the method disclosed in the examples described later, and its unit is mm.

[0031] The resin composition of the present invention may be insulating. That is, the resin composition can have insulation properties and / or form a cured product having insulation properties. For example, the dielectric breakdown voltage of the resin composition or its cured product measured in accordance with ASTM D149 may be about 3 kV / mm or more, about 5 kV / mm or more, about 7 kV / mm or more, 10 kV / mm or more, 15 kV / mm or more, or 20 kV / mm or more. The higher the value of the dielectric breakdown voltage, the better the insulation properties. The upper limit is not particularly limited, but considering the composition of the resin composition, etc., the dielectric 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. The dielectric breakdown voltage as described above can be adjusted and controlled by adjusting the insulation properties of the resin composition, and can be achieved, for example, by applying an insulating filler in the resin layer. Generally, among fillers, ceramic fillers are known as components that can ensure insulation properties.

[0032] The resin composition or its cured product may have flame retardancy. For example, the resin composition or its cured product can exhibit a V-0 rating in the UL94 V Test (Vertical Burning Test). This can ensure stability against fires and other accidents that are a concern depending on the application of the resin composition.

[0033] The resin composition or its cured product 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. A resin layer having a specific gravity within such a range is advantageous for providing a more lightweight product. The lower limit of the specific gravity is not particularly limited. For example, the specific gravity may be about 1.5 or more, or 2 or more. The components added to the resin layer to make the resin composition or its cured product exhibit the specific gravity can be adjusted. For example, when adding a filler, a filler that can ensure the desired properties (such as 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 surface-treated filler can be used.

[0034] The resin composition may have a low shrinkage rate during or after the curing process. Through this, it is possible to prevent peeling, void generation, etc. that may occur during the application process. The shrinkage rate can 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 numerical value of the shrinkage rate, the more advantageous it is, the lower limit is not particularly limited.

[0035] The resin composition or its cured product may have a low coefficient of thermal expansion (CTE). Through this, it is possible to prevent the occurrence of peeling, voids, etc. that may occur during application or use. The coefficient of thermal expansion can be appropriately adjusted within a range that can exhibit 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 about less than 100 ppm / K. Since the lower the numerical value of the coefficient of thermal expansion, the more advantageous it is, the lower limit is not particularly limited.

[0036] The resin composition or its cured product may also have a 5% weight loss temperature in thermogravimetric analysis (TGA) of 400°C or higher, and a remaining amount at 800°C of 70% by weight or higher. Such characteristics can further improve the high-temperature stability. In other examples, the remaining amount at 800°C may be about 75% by weight or higher, about 80% by weight or higher, about 85% by weight or higher, or about 90% by weight or higher. In other examples, the remaining amount at 800°C may be about 99% by weight or less. The thermogravimetric analysis (TGA) can be measured within 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 results of the thermogravimetric analysis (TGA) can also be achieved through the adjustment of the composition of the resin composition. For example, the remaining amount at 800°C usually depends on the type and ratio of the filler contained in the resin composition. When an excessive amount of filler is contained, the remaining amount increases.

[0037] The resin composition of the present invention may contain a curable component. The term "curable component" means a component containing one or more compounds containing functional groups that can participate in a curing reaction. In one example, the functional group that can participate in the curing reaction may be a hydroxy group. Therefore, the curable component may contain a reactive compound having a hydroxy group. In the above, the reactive compound means a compound having the hydroxy group and capable of participating in the curing reaction. Such a reactive compound may be a monomolecular, oligomeric, or polymeric compound.

[0038] The reactive compound having the hydroxy group may be a monofunctional compound or a polyfunctional compound. The term "monofunctional compound" means the reactive compound containing one hydroxy group per molecule, and the term "polyfunctional compound" means the reactive compound containing two or more hydroxy groups per molecule.

[0039] Further, the reactive compound having the hydroxy group may be an oil-modified compound described later, or may be a non-oil-modified compound. The oil-modified compound may be the monofunctional compound or the polyfunctional compound, and the non-oil-modified compound may also be the monofunctional compound or the polyfunctional compound.

[0040] The polyfunctional compound is also referred to as a polyol compound in this specification. The number of the hydroxy groups contained in the polyfunctional compound (polyol compound) is not particularly limited. In one example, the lower limit of the number of the hydroxy groups contained in the polyfunctional compound (polyol compound) may be 2 or 3 per molecule. The number of the hydroxy groups contained in the polyfunctional compound (polyol compound) may be equal to or more than any one of the lower limits described above. The upper limit of the number of the hydroxy groups contained in the polyfunctional compound (polyol compound) may be about 10, 9, 8, 7, 6, 5, 4, 3 or 2 per molecule. The number of the hydroxy groups contained in the polyfunctional compound (polyol compound) may be equal to or less than any one of the upper limits described above. The number of the hydroxy groups contained in the polyfunctional compound (polyol compound) may be within the range of any one of the lower limits described above and any one of the upper limits described above. The number of the hydroxy groups contained in the polyol compound can 1 be confirmed by 1H NMR, 1 and the number of the hydroxy groups can be confirmed based on the peak existing in the region of 3 to 4 ppm in 1H NMR.

[0041] The reactive compound may be an oil-modified compound. The term "oil-modified compound" means a compound containing a hydroxy group and having a linear or branched hydrocarbon group with 3 or more carbon atoms at its end. Therefore, a reactive compound that does not contain a linear or branched hydrocarbon group with 3 or more carbon atoms at its end is also referred to as a non-oil-modified compound in this specification. Whether the reactive compound contains the hydrocarbon group can be confirmed by 1 1H NMR, and 1 the presence and number of the hydrocarbon group can be confirmed based on the peak in the region of 4 - 5 ppm in 1H NMR. By applying the oil-modified compound, it is possible to ensure low adhesion to a specific material while being formed of a polyurethane material and without using an adhesion-reducing component such as a plasticizer or minimizing its usage amount.

[0042] The lower limit of the number of carbon atoms of the linear or branched hydrocarbon group contained at the end of the oil-modified compound may be about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17. The number of carbon atoms may be equal to or greater than any one of the above-mentioned lower limits. The upper limit of the number of carbon atoms may be about 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, or 8. The number of carbon atoms may be equal to or less than any one of the above-mentioned upper limits. The number of carbon atoms may be within the range between any one of the above-mentioned lower limits and any one of the above-mentioned upper limits.

[0043] The linear or branched hydrocarbon group may or may not contain a double bond. When it contains a double bond, the double bond may be a conjugated double bond or a cis double bond.

[0044] Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, or an alkynyl group. In one example, the hydrocarbon group may be linked to the polyol compound via a carbonyl group or a carbonyloxy group. In this case, the hydrocarbon group may be an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, or an alkynylcarbonyloxy group. In the above, the number of carbon atoms of the alkyl group, alkenyl group, or alkynyl group may be any one of the lower limits of the number of carbon atoms of the linear or branched hydrocarbon group described above or more, any one of the upper limits of the number of carbon atoms of the linear or branched hydrocarbon group described above or less, or within the range between any one of the lower limits of the number of carbon atoms of the linear or branched hydrocarbon group described above and any one of the upper limits of the number of carbon atoms of the linear or branched hydrocarbon group described above.

[0045] The alkyl group, alkenyl group, or alkynyl group may be linear or branched and may be optionally substituted with one substituent. When a substituent is present, there are no particular restrictions on the type of substituent. For example, a halogen atom such as fluorine can be exemplified as the substituent.

[0046] In one example, the hydrocarbon group may be included in the substituent of Chemical Formula 1 below.

[0047]

Chemical formula

[0048] In Chemical Formula 1, R is a hydrocarbon group that is linear or branched.

[0049] In Chemical Formula 1, the * indicates that this part is linked to the polyol compound. Therefore, an oxygen atom may be linked to the polyol compound in the substituent of Chemical Formula 1.

[0050] In Chemical Formula 1, the specific types of the hydrocarbon groups represented by R are as described above. Therefore, the contents regarding the number, type, form, and substituents of the carbon atoms of the above-described hydrocarbon groups can be applied in the same manner as above.

[0051] The number of the hydrocarbon groups contained in the reactive compound is not particularly limited. For example, the lower limit of the number of the hydrocarbon groups contained in the reactive compound may be 1 or 2 per molecule of the compound. The upper limit of the number of the hydrocarbon groups contained in the reactive compound may be about 10, 9, 8, 7, 6, 5, 4, 3, or 2 per molecule of the compound. The number of the hydrocarbon groups may be within the range of any one of the above-described lower limits or more, any one of the above-described upper limits or less, or between any one of the above-described lower limits and any one of the above-described upper limits.

[0052] The oil-modified compound can have various forms as long as it contains the hydroxy group and the hydrocarbon group.

[0053] In one example, the oil-modified compound may be a compound in which at least a part of the hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene, or an alkyne is substituted with the hydroxy group and / or the hydrocarbon group. The number of carbon atoms of the hydrocarbon compound such as an alkane, an alkene, or an alkyne may be, for example, 1 to 20, 1 to 16, 1 to 8, or 4 to 6. Such hydrocarbon compounds such as an alkane, an alkene, or an alkyne may be linear, branched, or cyclic. Further, the hydroxy group and / or the hydrocarbon group may be substituted at the same carbon atom or other carbon atoms in the alkane, alkene, or alkyne.

[0054] In other examples, the reactive compound may be a compound having a polyester backbone or a polyether backbone. In such cases, the reactive compound may be an oligomeric compound or a polymeric compound.

[0055] In one example, when the reactive compound having a polyester backbone is a polyol compound, the compound is a so-called polyester polyol, and may be a polyol having a structure in which the hydrocarbon group is linked to such a polyester polyol.

[0056] Also, when the reactive compound having a polyether backbone is a polyol compound, the compound is a so-called polyether polyol, and may be a polyol having a structure in which the hydrocarbon group is linked to such a polyether polyol.

[0057] In one example, the polyester backbone may be a so-called polycaprolactone backbone, and the polyether backbone may be a so-called polyalkylene backbone.

[0058] In one example, the polyester backbone may be a backbone having a repeating unit represented by the following Chemical Formula 2.

[0059]

Chemical Formula

[0060] In Chemical Formula 2, X1 and X2 are each independently a single bond or an oxygen atom, L1 may be an alkylene group or an alkylidene group, and n is an arbitrary number.

[0061] As used herein, the term "single bond" means the case where no atom exists at that site.

[0062] In Chemical Formula 2, the alkylene group may, in one example, be an alkylene group having 2 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, 4 to 12 carbon atoms, or 4 to 8 carbon atoms, and this may be linear or branched.

[0063] In Chemical Formula 2, the alkylidene group may, in one example, be an alkylidene group having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, 4 to 12 carbon atoms, or 4 to 8 carbon atoms, and this may be linear or branched.

[0064] In this specification, the alkylene group and the alkylidene group both mean a divalent substituent formed by the removal of two hydrogen atoms from an alkane. The alkylene group is a divalent substituent formed by the removal of the two hydrogen atoms from other carbon atoms of the alkane, and the alkylidene group is a divalent substituent formed by the removal of the two hydrogen atoms from one carbon atom of the alkane, and they are thus distinguished from each other.

[0065] In one example, the polyester backbone may be a polycaprolactone backbone, and in this case, L1 in Chemical Formula 2 may be a linear alkylene group having 5 carbon atoms or a linear alkylidene group having 5 carbon atoms.

[0066] In Chemical Formula 2, n is an arbitrary number indicating the number of repeating units. The lower limit of n may be, for example, about 1, 2, 3, 4, or 4.5, and the upper limit may be about 25, 20, 15, 10, or 5. The n may be equal to or greater than any one of the aforementioned lower limits, equal to or less than any one of the aforementioned upper limits, or within the range between any one of the aforementioned lower limits and any one of the aforementioned upper limits.

[0067] The skeleton of Chemical Formula 2 may be a so-called carboxylic acid polyol skeleton or a caprolactone polyol skeleton. Such skeletons can be formed by known methods. For example, the skeleton of the carboxylic acid polyol can be formed by reacting components containing a carboxylic acid and a polyol (e.g., diol or triol, etc.), and the skeleton of the caprolactone polyol can be formed by reacting components containing caprolactone and a polyol (e.g., diol or triol, etc.). The carboxylic acid may be a dicarboxylic acid.

[0068] In the oil-modified compound having the skeleton of Chemical Formula 2, the hydroxy group or the aforementioned hydrocarbon group may be present at the terminal of the skeleton of Chemical Formula 2.

[0069] In such a case, the skeleton of Chemical Formula 2 can be represented by the following Chemical Formula 3.

[0070]

Chem.

[0071] In Chemical Formula 3, X1, X2, L1 and n are as defined in Chemical Formula 2, and R1 may be a hydroxy group or a substituent of the following Chemical Formula 4.

[0072]

Chem.

[0073] In Chemical Formula 4, X3 is a single bond or an oxygen atom, and R is the same as R in Chemical Formula 1.

[0074] In Chemical Formula 3, when R1 is a hydroxy group, X1 is a single bond, and X2 may be an oxygen atom. When R1 is a substituent of Chemical Formula 4, either one of X1 and X3 is a single bond, and the other one may be an oxygen atom.

[0075] In the oil-modified compound, the lower limit of the number of skeletons of the chemical formula 2 or 3 may be about 1 or 2, and the upper limit may be about 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of the skeletons may be within a range that is equal to or greater than any one of the lower limits described above, equal to or less than any one of the upper limits described above, or between any one of the lower limits described above and any one of the upper limits described above.

[0076] The oil-modified compound having the polyester skeleton can have a linear or branched structure.

[0077] In the above, the linear structure is a structure in which a main chain containing the skeleton of the chemical formula 2 or 3 exists and no other polymer chain is linked to the main chain, and the branched structure may be a form in which a chain containing the skeleton of the chemical formula 2 or 3 is bonded as a side chain to the main chain containing the skeleton of the chemical formula 2 or 3. In the above, the number of chains containing the skeleton of the chemical formula 2 or 3 linked as a side chain in the branched structure may be, for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1.

[0078] In one example, the oil-modified compound having the polyester skeleton may be a compound in which at least a part of hydrogen atoms of a hydrocarbon compound such as alkane, alkene, or alkyne is substituted with the hydroxy group and / or the skeleton of the chemical formula 3. The number of carbon atoms of the hydrocarbon compound such as alkane, alkene, or alkyne may be, for example, 1 to 20, 1 to 16, 1 to 8, or 4 to 6.

[0079] Such hydrocarbon compounds such as alkane, alkene, or alkyne may be linear, branched, or cyclic. Also, the hydroxy group and / or the skeleton of the chemical formula 3 may be substituted on the same carbon atom or on other carbon atoms in the alkane, alkene, or alkyne.

[0080] In one example, the polyether backbone may be a backbone having a repeating unit represented by the following Chemical Formula 5.

[0081] [Chemical Formula]

[0082] In Chemical Formula 5, X4 and X5 are each independently a single bond or an oxygen atom, L2 may be an alkylene group or an alkylidene group, and m is an arbitrary number.

[0083] In Chemical Formula 5, the alkylene group may, in one example, be an alkylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, which may be linear or branched.

[0084] In Chemical Formula 5, the alkylidene group may, in one example, be an 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, which may be linear or branched.

[0085] The meanings of the alkylene group and the alkylidene group are as described above.

[0086] In Chemical Formula 5, m is an arbitrary number indicating the number of repeating units, and may be, for example, a number within the range of 1 to 25.

[0087] In the oil-modified compound having the backbone of Chemical Formula 5, the hydroxy group or the hydrocarbon group described above may be present at the terminal of the backbone of Chemical Formula 5.

[0088] In such a case, the backbone of Chemical Formula 5 may be represented by the following Chemical Formula 6.

[0089] [Chemical Formula]

[0090] In Chemical Formula 6, X4, X5, L2, and m are as defined in Chemical Formula 5, and R2 may be a hydroxy group or a substituent of the following Chemical Formula 7.

[0091]

Chem.

[0092] In Chemical Formula 7, X6 is a single bond or an oxygen atom, and R is the same as R in Chemical Formula 1 above.

[0093] In Chemical Formula 6, when R2 is a hydroxy group, X4 is a single bond; when R2 is a substituent of Chemical Formula 7, either one of X4 and X6 is a single bond, and the other one is an oxygen atom.

[0094] The oil-modified compound may contain one or more or two or more skeletons of Chemical Formula 5 or 6 above. The skeletons of Chemical Formula 5 or 6 may be contained in the polyol compound in an amount of 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less.

[0095] The polyol compound having the polyether skeleton may have a linear or branched structure.

[0096] In the above, the linear structure is a structure in which a main chain containing the skeleton of Chemical Formula 5 or 6 exists and no other polymer chain is linked to the main chain; the branched structure may be a form in which a chain containing the skeleton of Chemical Formula 5 or 6 is bonded as a side chain to the main chain containing the skeleton of Chemical Formula 5 or 6. In the above, the number of chains containing the skeleton of Chemical Formula 5 or 6 linked as side chains in the branched structure may be, for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1.

[0097] In one example, the oil-modified compound having the polyether skeleton may be a compound in which at least a part of the hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene or an alkyne is substituted with a hydroxy group and / or the skeleton of Chemical Formula 5. The number of carbon atoms of the hydrocarbon compound such as the alkane, the alkene or the alkyne may be, for example, 1 to 20, 1 to 16, 1 to 8 or 4 to 6.

[0098] Such hydrocarbon compounds such as alkanes, alkenes or alkynes may be linear, branched or cyclic. Further, the hydroxy group and / or the skeleton of Chemical Formula 5 may be substituted on the same carbon atom in the alkane, alkene or alkyne, or may be substituted on other carbon atoms.

[0099] When the above-described oil-modified compound is an oligomeric or polymeric compound, the compound can have an appropriate level of molecular weight.

[0100] For example, the lower limit of the weight average molecular weight of the oligomeric or polymeric oil-modified compound may be about 100 g / mol, 200 g / mol, 300 g / mol, 400 g / mol, 500 g / mol, 600 g / mol or 700 g / mol, and the upper limit may be about 3,000 g / mol, 2,500 g / mol, 2,000 g / mol, 1,500 g / mol, 1,000 g / mol or 900 g / mol. The weight average molecular weight may be within a range that is not less than any one of the above-described lower limits, not more than any one of the above-described upper limits, or between any one of the above-described lower limits and any one of the above-described upper limits.

[0101] By applying the oil-modified compound as described above, the desired physical properties can be more effectively ensured.

[0102] The oil-modified compound may be present in an appropriate proportion within the resin composition. For example, the lower limit of the proportion of the oil-modified compound within the resin composition may be about 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt% or 85 wt%, and the upper limit may be about 95 wt%, 90 wt%, 85 wt%, 80 wt% or 75 wt%. The proportion may be not less than any one of the lower limits described above, not more than any one of the upper limits described above, or within the range between any one of the lower limits described above and any one of the upper limits described above.

[0103] The content of the oil-modified compound is the content within the one-component composition when the resin composition is a one-component type, and is the content within the part where the oil-modified compound is present when it is a two-component type composition. For example, when the two-component composition includes a physically separated main component part and a curing agent part, and the oil-modified compound is included in the main component part, the content of the oil-modified compound may be the content based on the total weight of the main component part. Further, when the resin composition includes a solvent and / or a filler, the content is the content based on the weight excluding the content of the solvent and the filler.

[0104] In another exemplification, when the resin composition includes a filler component described later, the lower limit of the weight ratio of the oil-modified compound to 100 parts by weight of the filler component may be about 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight, and the upper limit may be about 30 parts by weight, 28 parts by weight, 26 parts by weight, 24 parts by weight, 22 parts by weight, 20 parts by weight, 18 parts by weight, 16 parts by weight, 14 parts by weight, 12 parts by weight, 10 parts by weight, or 9 parts by weight. The ratio may be not less than any one of the lower limits described above, not more than any one of the upper limits described above, or within the range between any one of the lower limits described above and any one of the upper limits described above.

[0105] The ratio to the filler component is, when the resin composition is a one - component type, the ratio to 100 parts by weight of the total filler component contained in the resin composition, and when it is a two - component type, the ratio to 100 parts by weight of the total filler component present in the part (main component part or curing agent part) containing the oil - modified polyol.

[0106] The oil - modified compound can be synthesized through known synthetic methods. That is, the compound can be produced by reacting a compound capable of introducing the hydrocarbon group corresponding to the oil - modified part with a known polyol compound or alcohol compound. In the above, the polyol compound is a compound having two or more hydroxy groups per molecule, and the alcohol compound is a compound having one hydroxy group per molecule. In the above, examples of the compound capable of introducing a hydrocarbon group include saturated or unsaturated fatty acids, specifically, butyric acid, caproic acid, 2 - ethyl hexanoic acid, caprylic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, linoleic acid, oleic acid, etc., but are not limited thereto.

[0107] There are no special restrictions on the type of polyol or alcohol compound that reacts with the saturated or unsaturated fatty acid. For example, appropriate types among the general reactive compounds described later can be applied, but are not limited thereto.

[0108] The reactive compound having a hydroxy group may further contain a reactive compound different from the oil-modified compound. In such a case, the reactive compound does not contain the hydrocarbon group described above, that is, a linear or branched hydrocarbon group having 3 or more carbon atoms. For convenience, such a reactive compound is also referred to as a non-oil-modified compound in this specification.

[0109] The non-oil-modified compound also contains one or more hydroxy groups per molecule. The lower limit of the number of hydroxy groups contained in the non-oil-modified compound may be about 1, 2, or 3, and the upper limit may be about 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of the hydroxy groups may be within a range of any one of the lower limits described above or between any one of the upper limits described above or between any one of the lower limits described above and any one of the upper limits described above.

[0110] The non-oil-modified compound may also be a monomolecular, oligomeric, or polymeric compound.

[0111] The non-oil-modified compound can have various forms.

[0112] In one example, the non-oil-modified compound may be a polyester polyol. As the polyester polyol, for example, so-called carboxylic acid polyol or caprolactone polyol can be used.

[0113] In one example, the polyester polyol may be a skeleton having a repeating unit represented by the following Chemical Formula 8.

[0114]

Chemical formula

[0115] In Chemical Formula 8, X7 and X8 are each independently a single bond or an oxygen atom, L3 may be an alkylene group or an alkylidene group, and p is an arbitrary number.

[0116] In Chemical Formula 8, the alkylidene group may, in one example, be an alkylene group having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, 4 to 12 carbon atoms, or 4 to 8 carbon atoms, and this may be linear or branched.

[0117] In Chemical Formula 8, the alkylene group may, in one example, be an alkylene group having 2 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, 4 to 12 carbon atoms, or 4 to 8 carbon atoms, and this may be linear or branched.

[0118] When the polyester polyol is a polycaprolactone polyol, L3 in Chemical Formula 8 may be a linear alkylene group having 5 carbon atoms.

[0119] Also, in Chemical Formula 8, p is an arbitrary number indicating the number of repeating units, and may be, for example, a number within the range of 1 to 25.

[0120] The polyester polyol having the skeleton of Chemical Formula 8 may be a so-called carboxylic acid polyol or a polycaprolactone polyol. Such a polyol compound can be formed by a known method. For example, the carboxylic acid polyol can be formed by reacting a component containing a carboxylic acid and a polyol (e.g., a diol or a triol), and the polycaprolactone polyol can be formed by reacting a component containing caprolactone and a polyol (e.g., a diol or a triol). The carboxylic acid may be a dicarboxylic acid.

[0121] In the polyol compound having the skeleton of Chemical Formula 8, the hydroxy group may be present at the end of the skeleton of Chemical Formula 8 or at other sites of the polyester polyol.

[0122] When the non-oil-modified compound contains the skeleton of Chemical Formula 8, the lower limit of the number of such skeletons may be about 1 or 2, and the upper limit may be about 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1. The number of the skeletons may be within the range of any one of the lower limits described above or more, any one of the upper limits described above or less, or between any one of the lower limits described above and any one of the upper limits described above.

[0123] The polyol compound having the polyester skeleton may have a linear or branched structure.

[0124] In the above, the linear structure is a structure in which a main chain containing the skeleton of Chemical Formula 8 exists and no other polymer chain is linked to the main chain, and the branched structure may be a form in which a chain containing the skeleton of Chemical Formula 8 is bonded as a side chain to the main chain containing the skeleton of Chemical Formula 8. In the above branched structure, the number of the chains containing the skeleton of Chemical Formula 8 linked as side chains may be, for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1.

[0125] As the non-oil-modified compound, in other examples, a polyol having a polycaprolactone polyol unit or an alkanediol unit, a polyol unit, and a dicarboxylic acid unit can also be used. Such a polyol may be a mixture of the polycaprolactone polyol unit alkanediol; polyol and dicarboxylic acid, or may be a reactant thereof. At this time, examples of the alkanediol include diol compounds having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, or 4 to 12 carbon atoms such as 3-methyl-1,5-pentanediol, 1,9-nonanediol, or 1,6-hexanediol. Further, examples of the polyol unit include alkanes or polycarbons having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, or 4 to 12 carbon atoms substituted with 3 to 10, 3 to 9, 3 to 8, 3 to 7, 3 to 6, 3 to 5, or 3 to 4 hydroxy groups such as trimethylolpropane. Examples of the dicarboxylic acid include adipic acid, terephthalic acid, isophthalic acid, or sebacic acid. Such types of polyol compounds are known under product names such as P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F-2010, F-3010, P-2011, P-520, P-2020, P-1012, P-2012, P-630, P-2030, P-2050, or N-2010 of Kuraray Co., Ltd.

[0126] As the non-oil-modified compound as described above, a polyol having a weight average molecular weight in the range of 100 g / mol to 5,000 g / mol can be used. Through the application of such a polyol, the intended effect can be achieved more effectively.

[0127] The curable component of the curable composition of the present invention may be composed of any one of the above-described reactive compounds or may be composed of a mixture of two or more of them.

[0128] In one example, the curable component may include a monofunctional compound (also referred to as the first reactive compound) and a polyfunctional compound (also referred to as the second reactive compound) among the above-described reactive compounds. At this time, the monofunctional compound and the polyfunctional compound may each independently be the oil-modified compound or the non-oil-modified compound.

[0129] In such a case, the lower limit of the weight ratio of the monofunctional compound to 100 parts by weight of the polyfunctional compound may be, for example, about 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight or 95 parts by weight, and the upper limit may be, for example, about 200 parts by weight, 190 parts by weight, 180 parts by weight, 170 parts by weight, 160 parts by weight, 150 parts by weight, 140 parts by weight, 130 parts by weight, 120 parts by weight, 110 parts by weight or 105 parts by weight. The ratio may be within a range that is not less than any one of the above-described lower limits, not more than any one of the above-described upper limits, or between any one of the above-described lower limits and any one of the above-described upper limits.

[0130] In the above case, the curable component may include a reactive compound having two hydroxy groups (also referred to as the third reactive compound) and a reactive compound having three or more hydroxy groups (also referred to as the fourth reactive compound) as the second reactive compound. The upper limit of the number of hydroxy groups contained in the fourth reactive compound may be about 10, 9, 8, 7, 6, 5, 4 or 3 per molecule. The number of hydroxy groups of the fourth reactive compound is 3 or more and not more than any one of the above-described upper limits.

[0131] In such a case, the lower limit of the weight ratio of the fourth reactive compound to 100 parts by weight of the third reactive compound may be, for example, about 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight, and the upper limit may be, for example, about 20 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight or 12 parts by weight. The ratio may be within the range of not less than any one of the lower limits described above, not more than any one of the upper limits described above, or between any one of the lower limits described above and any one of the upper limits described above.

[0132] Each of the first to fourth reactive compounds may independently be the oil-modified compound described above or a non-oil-modified compound.

[0133] In a suitable example, among the first to fourth reactive compounds, the first reactive compound and the third reactive compound may be oil-modified compounds.

[0134] In such a case, the fourth reactive compound may be an oil-modified compound or a non-oil-modified compound, and may be a non-oil-modified compound in a suitable example. As the non-oil-modified compound, for example, the polycaprolactone polyol unit or the alkanediol unit described above; a compound containing a polyol unit and a dicarboxylic acid unit can be used.

[0135] In another example, the curable component may contain a polyfunctional compound (hereinafter also referred to as a fifth reactive compound) among the reactive compounds described above. At this time, each of the polyfunctional compounds may independently be the oil-modified compound or a non-oil-modified compound.

[0136] In the above case, the curable component may include, as the polyfunctional compound, a reactive compound having two hydroxy groups (hereinafter also referred to as the sixth reactive compound) and a reactive compound having three or more hydroxy groups (hereinafter also referred to as the seventh reactive compound). The upper limit of the number of hydroxy groups contained in the seventh reactive compound may be about 10, 9, 8, 7, 6, 5, 4, or 3 per molecule. The number of hydroxy groups of the seventh reactive compound is 3 or more and may be equal to or less than any one of the above-mentioned upper limits.

[0137] In such a case, the lower limit of the weight ratio of the seventh reactive compound to 100 parts by weight of the sixth reactive compound may be, for example, about 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or 11 parts by weight, and the upper limit may be, for example, about 20 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight, or 12 parts by weight. The ratio may be within the range of any one of the above-mentioned lower limits or between any one of the above-mentioned lower limits and any one of the above-mentioned upper limits.

[0138] The sixth and seventh reactive compounds may each independently be the above-mentioned oil-modified compound or a non-oil-modified compound.

[0139] In a suitable example, among the sixth and seventh reactive compounds, the sixth reactive compound may be an oil-modified compound.

[0140] In such a case, the seventh reactive compound may be an oil-modified compound or a non-oil-modified compound, and in a suitable example, it may be a non-oil-modified compound. As the non-oil-modified compound, for example, the above-mentioned polycaprolactone polyol unit or alkane diol unit; a compound containing a polyol unit and a dicarboxylic acid unit can be used.

[0141] The resin composition may further contain, as an additional component, a curing agent that reacts with the curable component, for example.

[0142] As the curing agent, various types can be applied. However, in the case of a polyurethane composition that is a resin composition, as the curing agent, polyisocyanate (also referred to as a polyisocyanate compound) can be applied. The term "polyisocyanate" means a compound having two or more isocyanate groups. The lower limit of the number of isocyanate groups of the polyisocyanate may be about 2 or 3, and the upper limit may be about 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of isocyanate groups may be within the range of any one of the lower limits described above or within the range between any one of the upper limits described above or any one of the lower limits described above and any one of the upper limits described above.

[0143] The type of polyisocyanate used as the curing agent is not particularly limited. However, in order to ensure the desired physical properties, a non-aromatic polyisocyanate that does not contain an aromatic group can be used.

[0144] Further, if necessary, both a bifunctional polyisocyanate and a polyisocyanate having three or more functional groups can be applied as the polyisocyanate. In the above, bifunctional means that the compound contains two isocyanate groups, and trifunctional means that the compound contains three or more isocyanate groups.

[0145] Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate, or tetramethylene diisocyanate; alicyclic polyisocyanates such as trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane diisocyanate, or dicyclohexylmethane diisocyanate; or carbodiimide-modified polyisocyanates, isocyanurate-modified polyisocyanates, or the like of any one or more of the above. Further, as the polyisocyanate, an addition reaction product of the above-described diisocyanate and a polyol (e.g., trimethylolpropane) can also be used. Further, a mixture of two or more of the listed compounds can be used.

[0146] The application ratio of the polyisocyanate can be adjusted in consideration of the number of hydroxy groups present in the curable component contained in the resin composition and the physical properties after curing.

[0147] For example, the polyisocyanate can be included in the resin composition such that the equivalent ratio (OH / NCO) of the number of hydroxy groups (OH) present in the curable component and the number of isocyanate groups (NCO) present in the polyisocyanate is within a predetermined range.

[0148] The method for calculating the equivalent ratio (OH / NCO) is known.

[0149] For example, when the resin composition is a two-component type, the curable component is contained in the main agent part, and the polyisocyanate is contained in the curing agent part, the equivalent ratio OH / NCO can be calculated by the following general formula 1.

[0150]

Number

[0151] In General Formula 1, E is the equivalent ratio OH / NCO, and D m is the density of the main component part, and D c is the density of the curing agent part. A is obtained by the following General Formula 2, B is obtained by the following General Formula 3, and D NCO is 42 Da as the Dalton mass of the isocyanate group, and D OH is 17 Da as the Dalton mass of the hydroxy group.

[0152]

Number

[0153] In General Formula 2, W OH is the weight ratio of the reactive compound present in the main component part, and OH % is the ratio of the hydroxy groups contained in the reactive compound having the weight ratio of W OH is the ratio of the hydroxy groups contained in the reactive compound having the weight ratio of W.

[0154]

Number

[0155] In General Formula 3, W NCO is the weight ratio of the polyisocyanate present in the curing agent part, and NCO % is the ratio of the isocyanate groups contained in the polyisocyanate having the weight ratio of W NCO is the ratio of the isocyanate groups contained in the polyisocyanate having the weight ratio of W.

[0156] In the above, W OH is the weight % (based on the total weight of the main component part) of each reactive compound present in the main component part. The OH% of the compound is the % of the hydroxy groups contained in 1 mole of each reactive compound, and is obtained by multiplying the product of the number of moles of the hydroxy groups contained in a single reactive compound and the molar mass of the hydroxy group by 100 after dividing by the molar mass of the single reactive compound.

[0157] In the above, W NCOis the weight % in the hardener part of each polyisocyanate present in the hardener part (based on the total weight of the hardener part), and the NCO of the compound % is the % of NCO groups contained in 1 mol of each polyisocyanate, and is obtained by multiplying the number of moles of NCO groups contained in a single polyisocyanate by the molar mass of the NCO groups, dividing the product by the molar mass of the single polyisocyanate, and then multiplying by 100.

[0158] In General Formula 1, the Dalton mass is a constant.

[0159] The lower limit of the equivalent ratio (OH / NCO) may be, for example, about 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250 or 260, and the upper limit may be, for example, about 1,000, 900, 800, 700, 600, 500, 400, 300, 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110 or 100. The equivalent ratio may be within the range of any one of the lower limits described above or above any one of the lower limits, any one of the upper limits described above or below any one of the upper limits, or between any one of the lower limits described above and any one of the upper limits described above.

[0160] The resin composition may further contain a filler component. The term "filler component" means a component consisting of a filler, that is, a component containing only a filler.

[0161] In one example, the filler component may include two or more fillers having different average particle sizes from each other. In one example, the filler component may include three or more fillers having different average particle sizes from each other, or may be composed of three to six, three to five, three to four, or three fillers having different average particle sizes from each other. That is, in one example, the filler component may also include only three to six, three to five, three to four, or three fillers having different average particle sizes from each other.

[0162] In another example, the filler component can exhibit at least two peaks in the volume curve of the particle size distribution measured using the laser diffraction method. In one example, the filler component can exhibit three or more peaks in the volume curve of the particle size distribution, or can exhibit three to six, three to five, three to four, or three peaks. For example, in the range of filler components showing three peaks, filler components showing one, two, or four or more peaks are not included.

[0163] The average particle size of the filler of the present invention means the particle size at which the volume accumulation becomes 50% in the volume curve of the particle size distribution measured by the laser diffraction method, which is also called the median diameter. That is, in the present invention, the particle size distribution is determined on a volume basis through the laser diffraction method, and the particle size at the point where the cumulative value becomes 50% in the cumulative curve with the total volume as 100% is defined as the average particle size. Such an average particle size is called the median diameter or D50 particle size in other examples.

[0164] Therefore, the two fillers having different average particle sizes as described above can mean fillers having different particle sizes at the point where the cumulative value becomes 50% in the volume curve of the particle size distribution.

[0165] Generally, when mixing two or more fillers having different average particle sizes to form a filler component, in the volume curve of the particle size distribution measured using the laser diffraction method for the filler component, peaks corresponding to the types of the mixed fillers appear. Therefore, for example, when mixing three fillers having different average particle sizes to form a filler component, the volume curve of the particle size distribution measured using the laser diffraction method for the filler component shows three peaks.

[0166] The filler component of the resin composition of the present invention may be a thermally conductive filler component. The term "thermally conductive filler component" means a filler component that functions such that the resin composition or its cured product exhibits the above-described thermal conductivity.

[0167] In one example, the filler component may include at least a first filler having an average particle size of 60 μm to 200 μm, a second filler having an average particle size in the range of 10 μm to 30 μm, and a third filler having an average particle size of 5 μm or less.

[0168] In other examples, the first filler may have an average particle size of about 62 μm or more, 64 μm or more, 66 μm or more, or about 68 μm or more, and / or about 195 μm or less, 190 μm or less, 185 μm or less, 180 μm or less, 175 μm or less, 170 μm or less, 165 μm or less, 160 μm or less, 155 μm or less, 150 μm or less, 145 μm or less, 140 μm or less, 135 μm or less, 130 μm or less, 125 μm or less, about 120 μm or less, 115 μm or less, 110 μm or less, 105 μm or less, 100 μm or less, 95 μm or less, 90 μm or less, 85 μm or less, 80 μm or less, or about 75 μm or less.

[0169] In other examples, the second filler may have an average particle size of about 12 μm or more, 13 μm or more, 14 μm or more, 15 μm or more, 16 μm or more, 17 μm or more, 18 μm or more, 19 μm or more, or 20 μm or more, and / or about 29 μm or less, 28 μm or less, 27 μm or less, 26 μm or less, 25 μm or less, 24 μm or less, 23 μm or less, 22 μm or less, 21 μm or less, or about 20 μm or less.

[0170] In other examples, the third filler may have an average particle size of about 0.01 μm or more, 0.1 μm or more, about 0.5 μm or more, 1 μm or more, 1.5 μm or more, or 2 μm or more, and / or about 5 μm or less, 4.5 μm or less, about 4 μm or less, 3.5 μm or less, 3 μm or less, 2.5 μm or less, or about 2 μm or less.

[0171] In the filler component, the ratio (D1 / D3) of the average particle size (D1) of the first filler to the average particle size (D3) of the third filler can be in the range of 25 to 300.

[0172] In one example, when the filler component contains two or more fillers with different average particle sizes from each other, the third filler may be the filler with the smallest average particle size among the fillers contained in the filler component, and the first filler may be the filler with the largest average particle size among the fillers contained in the filler component. In such a state, the particle size ratio can be satisfied.

[0173] In other examples, the ratio (D1 / D3) can be further adjusted within the range of 26 or more, 27 or more, 28 or more, 29 or more, 30 or more, 31 or more, 32 or more, 33 or more, 34 or more, 35 or more, 40 or more, 50 or more, 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 or 235 or more and / or within the range of 290 or less, 280 or less, 270 or less, 260 or less, 250 or less, 240 or less, 220 or less, 200 or less, 180 or less, 160 or less, 140 or less, 120 or less, about 100 or less, 95 or less, 90 or less, 85 or less, 80 or less, about 75 or less, 70 or less, 65 or less or about 60 or less.

[0174] In the filler component, the ratio (D1 / D2) of the average particle size (D1) of the first filler to the average particle size (D2) of the second filler may be within the range of about 3 to 20. In other examples, the ratio (D1 / D2) may be 3.1 or more, 3.2 or more, 3.3 or more, 3.4 or more or 3.5 or more, or may be about 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less or 4 or less.

[0175] As the filler, for example, ceramic fillers such as aluminum oxide (alumina: Al2O3), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si3N4), silicon carbide (SiC), beryllium oxide (BeO), zinc oxide (ZnO), magnesium oxide (MgO), aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), calcium carbonate (CaCO3) and / or boehmite can be used. Such fillers are advantageous for satisfying the thermal conductivity in the aforementioned range, and can further satisfy the insulation properties and the like described above through the application of ceramic fillers.

[0176] The upper limit of the proportion of the filler component in the resin composition may be about 95% by weight, 94.5% by weight, 94% by weight, 93.5% by weight, 93% by weight, 92.5% by weight, 92% by weight, 91.5% by weight, 91% by weight, 90.5% by weight, 90.0% by weight, 89.5% by weight or 89.0% by weight, and the lower limit thereof may be about 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, about 75% by weight, 76% by weight, 77% by weight, 78% by weight, 79% by weight, 80% by weight, 81% by weight, 82% by weight, 83% by weight, 84% by weight, 85% by weight, 86% by weight, 87% by weight or 88% by weight. The proportion may be within the range of any one of the aforementioned lower limits or more, any one of the aforementioned upper limits or less, or between any one of the aforementioned lower limits and any one of the aforementioned upper limits.

[0177] The lower limit of the proportion of the filler component with respect to 100 parts by weight of the total weight of the curable component or the reactive compound present in the curable component may be about 500 parts by weight, 550 parts by weight, 600 parts by weight, 650 parts by weight, 700 parts by weight, 750 parts by weight, 800 parts by weight, 850 parts by weight, 900 parts by weight, 950 parts by weight, or 1,000 parts by weight, and the upper limit thereof may be about 2,000 parts by weight, 1,800 parts by weight, 1,600 parts by weight, 1,400 parts by weight, 1,200 parts by weight, 1,100 parts by weight, 1,000 parts by weight, 950 parts by weight or 900 parts by weight. The proportion may be within the range of any one of the aforementioned lower limits or more, any one of the aforementioned upper limits or less, or between any one of the aforementioned lower limits and any one of the aforementioned upper limits.

[0178] The content of the filler component is a proportion based on the total weight of the resin composition when the resin composition is a one-component composition, and may be a proportion based on the total weight of the main agent part and the curing agent part of the two-component resin composition, or may be a proportion based on the total weight of the main agent or the curing agent part alone.

[0179] When the resin composition is a two - component composition, it is appropriate to divide the filler component to be applied to the final cured body into substantially the same amount and introduce it into each of the main agent and the curing agent parts.

[0180] In addition to the thermally conductive filler, the filler component may, if necessary, contain various types of fillers. For example, carbon fillers such as graphite, fumed silica, or clay can also be applied.

[0181] In addition to the components described above, the resin composition may further contain necessary components.

[0182] In one example, the resin composition may further contain a plasticizer. As described above, in the present invention, a low adhesive force can be ensured for a specific material without applying a plasticizer, but a small amount of plasticizer can also be applied if necessary.

[0183] There are no special restrictions on the types of applicable plasticizers. For example, phthalate - based plasticizers such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), diisononyl phthalate (DINP), or polyethylene terephthalate (PET), adipate - based plasticizers such as dioctyl adipate (DOA) or diisononyl adipate (DINA), fatty acid - based plasticizers, phosphate - based plasticizers, or polyester - based plasticizers can be applied.

[0184] When a plasticizer is included, its proportion can be adjusted according to the purpose. For example, the lower limit of the proportion of the plasticizer relative to 100 parts by weight of the total weight of the curable component or the reactive compound present in the curable component may be about 0.5 part by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 13.5 parts by weight, 14 parts by weight or 14.5 parts by weight, and the upper limit may be about 40 parts by weight, 39 parts by weight, 38 parts by weight, 37 parts by weight, 36 parts by weight, 35 parts by weight, 34 parts by weight, 33 parts by weight, 32 parts by weight, 31 parts by weight, 30 parts by weight, 29 parts by weight, 28 parts by weight, 27 parts by weight, 26 parts by weight, 25 parts by weight, 24 parts by weight, 23 parts by weight, 22 parts by weight, 21 parts by weight, 10 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight or 15 parts by weight. The proportion may be within the range of any one of the above-mentioned lower limits or between any one of the above-mentioned lower limits and any one of the above-mentioned upper limits. The proportion can also be changed in consideration of the composition of the entire resin composition and the intended use.

[0185] The resin composition may further contain a catalyst as an additional component. The type of catalyst that can be included is not particularly limited as long as it can induce appropriate curing depending on the type of the curable component. For example, when the resin composition is a polyurethane composition and the curable component is a component that forms polyurethane, a urethane reaction catalyst can be applied as the catalyst.

[0186] As the urethane reaction catalyst, known components can be used without special restrictions, and examples thereof include organic catalysts such as tertiary amines and organometallic catalysts. From the viewpoint of exerting appropriate effects through combination with the curing rate retarder described later, as the catalyst, an organometallic catalyst can be applied, and for example, a tin catalyst such as an organotin catalyst can be used.

[0187] When the catalyst is included, its ratio can be adjusted according to the purpose. For example, the lower limit of the ratio of the catalyst to 100 parts by weight of the total weight of the curable component or the reactive compound present in the curable component may be about 0.001 part by weight, 0.005 part by weight, 0.01 part by weight, 0.05 part by weight, 0.1 part by weight, 0.5 part by weight or 0.55 part by weight, and the upper limit may be about 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight or 0.5 part by weight. The ratio may be within the range of any one of the lower limits described above or between any one of the upper limits described above or between any one of the lower limits described above and any one of the upper limits described above. The ratio can also be changed in consideration of the composition of the entire resin composition and the intended use.

[0188] The resin composition may contain a curing rate regulator to ensure an appropriate curing rate. In the present invention, the term "curing rate regulator" means a component that can delay the curing rate of the resin composition compared to the case where the component is not present. Usually, the curing of the resin composition starts to be induced when the components participating in the curing reaction are mixed under curable conditions. For example, when the resin composition is a room temperature curing type and is a two-component type containing a main agent part and a curing agent part, the resin composition starts to cure when the main agent and the curing agent parts are mixed at room temperature.

[0189] By the way, depending on the use of the resin composition, problems may occur when the curing rate is too fast after the start of curing as described above.

[0190] Therefore, in the present invention, when necessary, the curing rate regulator can be applied to ensure an appropriate curing rate. There are no particular restrictions on the type of curing rate regulator applied in this case. For example, a component that can react competitively with the curable components and catalysts contained in the resin composition or show an affinity and exhibit an effect of adjusting the curing rate can be applied.

[0191] When the resin composition is a polyurethane composition, a thiol compound or a carboxylic acid compound can be used as the curing rate regulator. As the curing rate regulator, either one of the thiol compound and the carboxylic acid compound can be used, or both can be used.

[0192] As the thiol compound, for example, a compound represented by the following Chemical Formula 9 can be used.

[0193]

Chemical Formula

[0194] In Chemical Formula 9, R1 may be an alkyl group, an alkoxy group, an aromatic monovalent hydrocarbon group, or -Si(R3)3, R2 may be a single bond, an alkylene group, or an alkylidene group, and the R3 may be hydrogen, an alkyl group, or an alkoxy group.

[0195] In Chemical Formula 9, the fact that R2 is a single bond means a structure in which R2 does not exist and the thiol (SH) group is directly connected to R1.

[0196] The alkyl group of R1 or R3 in Chemical Formula 9 may be an alkyl 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. Such an alkyl group may be linear, branched, or cyclic. The alkyl group may optionally be substituted with one or more substituents or may be unsubstituted. When substituted, examples of the substituent include, but are not limited to, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, or a thiol group.

[0197] The alkoxy group of R1 or R3 in Chemical Formula 9 may be an alkoxy 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. Such an alkoxy group may be linear, branched, or cyclic. The alkoxy group may optionally be substituted with one or more substituents or may be unsubstituted. When substituted, examples of the substituent include, but are not limited to, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a thiol group.

[0198] In the above, examples of the aromatic monovalent hydrocarbon group include an aryl group or a heteroaryl group. At this time, examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a phenalenyl group, a chrysenyl group, or a fluorenyl group, etc. Examples of the heteroaryl group include 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 pyrimidinyl group, a triazine group, an acridyl group, a pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, an isoquinolin group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, or a dibenzofuranyl group, etc., but are not limited thereto. Such an aromatic monovalent hydrocarbon group may be optionally substituted with one or more substituents, or may be unsubstituted. When substituted, examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a thiol group, etc., but are not limited thereto.

[0199] In Chemical Formula 9, the alkylene group of R2 may, in one example, be an alkylene group having 2 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, 4 to 12 carbon atoms, or 4 to 8 carbon atoms, and this may be linear or branched. Such an alkylene group may be optionally substituted with one or more substituents, or may be unsubstituted. When substituted, examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a thiol group, etc., but are not limited thereto. Also, in some cases, at least one of the carbon atoms constituting the alkylene group may be substituted with an oxygen atom.

[0200] In one example, the alkylidene group of R2 in Chemical Formula 9 may be an alkylidene group having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, 4 to 12 carbon atoms, or 4 to 8 carbon atoms, which may be linear or branched. Such an alkylidene group may be optionally substituted with one or more substituents or may be unsubstituted. When it is substituted, examples of the substituent include, but are not limited to, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a thiol group. Also, in some cases, at least one of the carbon atoms constituting the alkylidene group may be substituted with an oxygen atom.

[0201] As the thiol compound, for example, a monofunctional compound having a hydrocarbon group can be used. The hydrocarbon group may be a substituted or unsubstituted hydrocarbon group. When the hydrocarbon group is a substituted hydrocarbon group, the type of the substituent is not particularly limited, and examples thereof include a halogen, an alkoxy group having 1 to 4 carbon atoms, and / or a silyl group (for example, a substituent represented by -Si(R3)3 in Chemical Formula 9). The fact that the thiol compound is a monofunctional compound means that the compound contains one thiol group (-SH).

[0202] The hydrocarbon group of the thiol compound may be an alkyl group, an alkenyl group, or an alkynyl group. At this time, the alkyl group may be an alkyl group having 1 to 30 carbon atoms, 4 to 30 carbon atoms, 8 to 30 carbon atoms, 8 to 26 carbon atoms, 8 to 22 carbon atoms, 8 to 18 carbon atoms, or 8 to 14 carbon atoms, and this alkyl group may be linear or branched. The alkenyl group or alkynyl group may be an alkenyl group or alkynyl group having 2 to 30 carbon atoms, 4 to 30 carbon atoms, 8 to 30 carbon atoms, 8 to 26 carbon atoms, 8 to 22 carbon atoms, 8 to 18 carbon atoms, or 8 to 14 carbon atoms, and this alkenyl group or alkynyl group may be linear or branched.

[0203] The thiol compound may be a compound in which one of the hydrogen atoms of a hydrocarbon compound such as alkane, alkene or alkyne is substituted with a thiol group (-SH). In such a case, the alkane may be an alkane having 1 to 30 carbon atoms, 4 to 30 carbon atoms, 8 to 30 carbon atoms, 8 to 26 carbon atoms, 8 to 22 carbon atoms, 8 to 18 carbon atoms or 8 to 14 carbon atoms, and this alkane may be linear or branched. The alkene or alkyne may be an alkene or alkyne having 2 to 30 carbon atoms, 4 to 30 carbon atoms, 8 to 30 carbon atoms, 8 to 26 carbon atoms, 8 to 22 carbon atoms, 8 to 18 carbon atoms or 8 to 14 carbon atoms, and this alkene or alkyne may be linear or branched.

[0204] The alkane, alkene or alkyne may optionally be substituted with other substituents in addition to the thiol group if necessary. In such a case, examples of the substituents include, but are not limited to, alkoxy groups having 1 to 4 carbon atoms and / or silyl groups (for example, the substituent represented by -Si(R3)3 in Chemical Formula 9 above).

[0205] The lower limit of the molecular weight (molar mass) of the thiol compound may be about 50 g / mol, 100 g / mol, 150 g / mol or 200 g / mol, and the upper limit may be about 400 g / mol, 350 g / mol, 300 g / mol or 250 g / mol. The molecular weight may be within the range of any one of the lower limits described above or between any one of the lower limits and any one of the upper limits described above.

[0206] There are no particular restrictions on the specific types of the thiol compounds as described above, and for example, 1-dodecane thiol or (3-mercaptopropyl)triethoxy silane may be used.

[0207] When a thiol compound is included, its proportion can be adjusted according to the purpose. For example, the lower limit of the proportion of the thiol compound with respect to 100 parts by weight of the total weight of the curable component or the reactive compound present in the curable component may be about 0.001 part by weight, 0.005 part by weight, 0.01 part by weight, 0.05 part by weight, 0.1 part by weight, 0.5 part by weight, 1 part by weight or 1.5 parts by weight, and the upper limit may be about 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight, 0.9 part by weight, 0.8 part by weight, 0.7 part by weight, 0.6 part by weight, 0.5 part by weight, 0.4 part by weight, 0.3 part by weight or 0.2 part by weight. The proportion may be within the range of any one of the lower limits described above or more, any one of the upper limits described above or less, or between any one of the lower limits described above and any one of the upper limits described above.

[0208] The proportion can also be changed in consideration of the composition of the entire resin composition and the intended use.

[0209] When the thiol compound and the catalyst are simultaneously included in the polyurethane composition, their proportions can be controlled.

[0210] For example, the lower limit of the weight ratio (T / U) of the thiol compound (T) to the urethane reaction catalyst (U) may be 0.1, 0.5, 1, 1.5, 2, 2.5 or 3, and the upper limit thereof may be about 6, 5.5, 5, 4.5, 4 or 3.5. The ratio (T / U) may be within the range of any one of the lower limits described above or more, any one of the upper limits described above or less, or between any one of the lower limits described above and any one of the upper limits described above.

[0211] In the above, as the carboxylic acid compound, for example, it may be a monofunctional compound having a hydrocarbon group. The fact that the carboxylic acid compound is a monofunctional compound means that the compound contains one carboxyl group (-COOH).

[0212] In one example, the carboxylic acid compound may be, for example, a carboxylic acid compound in which the hydrocarbon group is a saturated hydrocarbon group. Such a carboxylic acid compound may be, for example, a non-aromatic carboxylic acid compound. Such a carboxylic acid compound may be, for example, a compound in which the carbonyl group of the carboxylic acid compound is not conjugated with a π-electron system.

[0213] The hydrocarbon group of the carboxylic acid compound may be an alkyl group, an alkenyl group or an alkynyl group. At this time, the alkyl group may be an alkyl group having 1 to 30 carbon atoms, 1 to 26 carbon atoms, 1 to 22 carbon atoms, 1 to 18 carbon atoms, 1 to 14 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 4 to 30 carbon atoms, 5 to 30 carbon atoms, 5 to 26 carbon atoms, 5 to 22 carbon atoms, 5 to 18 carbon atoms, 5 to 14 carbon atoms or 5 to 10 carbon atoms, and this alkyl group may be linear or branched. The alkenyl group or alkynyl group may be an alkenyl group or alkynyl group having 2 to 30 carbon atoms, 4 to 30 carbon atoms, 5 to 30 carbon atoms, 5 to 26 carbon atoms, 5 to 22 carbon atoms, 5 to 18 carbon atoms, 5 to 14 carbon atoms or 5 to 10 carbon atoms, and this alkenyl group or alkynyl group may be linear or branched.

[0214] The carboxylic acid compound may be a compound in which one of the hydrogen atoms in a hydrocarbon compound such as an alkane, alkene or alkyne is substituted with a carboxyl group (-COOH). In such a case, the alkane may be an alkane having 1 to 30 carbon atoms, 1 to 26 carbon atoms, 1 to 22 carbon atoms, 1 to 18 carbon atoms, 1 to 14 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 4 to 30 carbon atoms, 5 to 30 carbon atoms, 5 to 26 carbon atoms, 5 to 22 carbon atoms, 5 to 18 carbon atoms, 5 to 14 carbon atoms or 5 to 10 carbon atoms, and this alkane may be linear or branched. The alkene or alkyne may be an alkene or alkyne having 2 to 30 carbon atoms, 4 to 30 carbon atoms, 5 to 30 carbon atoms, 5 to 26 carbon atoms, 5 to 22 carbon atoms, 5 to 18 carbon atoms, 5 to 14 carbon atoms or 5 to 10 carbon atoms, and this alkene or alkyne may be linear or branched.

[0215] The lower limit of the molecular weight (molar mass) of the carboxylic acid compound may be about 50 g / mol, 70 g / mol, 90 g / mol, 110 g / mol, 130 g / mol or 140 g / mol, and the upper limit may be about 400 g / mol, 350 g / mol, 300 g / mol, 250 g / mol, 200 g / mol, 150 g / mol or 100 g / mol. The molecular weight may be not less than any one of the lower limits described above, not more than any one of the upper limits described above, or within the range between any one of the lower limits described above and any one of the upper limits described above.

[0216] As the carboxylic acid compound, a compound having a pKa within a predetermined range can be applied. The lower limit of the pKa of the compound may be about 2, 2.5, 3, 3.5, 4 or 4.5, and the upper limit may be about 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5 or 5. The pKa may be equal to or higher than any one of the lower limits described above, equal to or lower than any one of the upper limits described above, or within the range between any one of the lower limits described above and any one of the upper limits described above. The ratio can also be changed in consideration of the composition of the entire resin composition and the intended use.

[0217] There are no particular restrictions on the specific type of the carboxylic acid compound, and for example, it may be acetic acid, stearic acid, 2-ethylhexanoic acid, isononanoic acid, oleic acid, or the like.

[0218] When a carboxylic acid compound is included, its ratio can be adjusted according to the purpose. For example, the lower limit of the ratio of the carboxylic acid compound to 100 parts by weight of the total weight of the curable component or the reactive compound present in the curable component may be about 0.001 part by weight, 0.005 part by weight, 0.01 part by weight, 0.05 part by weight, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight or 3.5 parts by weight, and the upper limit may be about 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight, 0.9 part by weight, 0.8 part by weight, 0.7 part by weight, 0.6 part by weight, 0.5 part by weight, 0.4 part by weight, 0.3 part by weight or 0.2 part by weight. The ratio may be equal to or higher than any one of the lower limits described above, equal to or lower than any one of the upper limits described above, or within the range between any one of the lower limits described above and any one of the upper limits described above. The ratio can also be changed in consideration of the composition of the entire resin composition and the intended use.

[0219] In the polyurethane composition, when the carboxylic acid compound and the catalyst are contained simultaneously, their ratios can be controlled.

[0220] For example, the lower limit of the weight ratio (C / U) of the carboxylic acid compound (C) to the urethane reaction catalyst (U) may be 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5 or 5.5, and the upper limit thereof may be about 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5.5, 5, 4.5, 4, 3.5, 3, 3.5, 2, 2.5 or 1. The ratio (C / U) may be within the range of any one of the lower limits described above or more, any one of the upper limits described above or less, or between any one of the lower limits described above and any one of the upper limits described above.

[0221] As described above, as the curing rate regulator, either one or both of the thiol compound and the carboxylic acid compound can be applied. In order to secure a target viscosity maintenance period after the start of curing, secure an appropriate curing rate and curing ability after the lapse of the viscosity maintenance period, and simultaneously enable adjustment of the hardness increase rate, the carboxylic acid compound and the thiol compound can be applied simultaneously.

[0222] When the thiol compound and the carboxylic acid compound are contained simultaneously as described above, the weight ratio (T / C) of the thiol compound (T) to the carboxylic acid compound (C) can be adjusted. The lower limit of the ratio (T / C) may be about 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5 or 3, and the upper limit may be about 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.5, 3, 2.5, 2 or 1.5. The ratio (T / C) may be within the range of any one of the lower limits described above or more, any one of the upper limits described above or less, or between any one of the lower limits described above and any one of the upper limits described above.

[0223] The resin composition contains the above components, and may further contain other components if necessary. Examples of other components applied in this case include viscosity modifiers for adjusting viscosity, for example, increasing or reducing viscosity, or adjusting viscosity by shear force (e.g., thixotropic agents, diluents, etc.), dispersants, surface treatment agents, flame retardants, flame retardant aids, and / or coupling agents, etc., but are not limited thereto.

[0224] As described above, the resin composition may be a one-component composition or a two-component composition.

[0225] In the case of a two-component composition, each of the above-described components of the resin composition may be contained in physically separated main agent parts and curing agent parts.

[0226] In one exemplary embodiment, the present invention relates to a composition (two-component composition) in which the resin composition is a two-component composition.

[0227] Such a two-component composition may contain at least main agent parts and curing agent parts, and the main agent and curing agent parts may be physically separated from each other. When the physically separated main agent and curing agent parts are mixed, a curing reaction may be initiated. When the resin composition is a polyurethane composition, polyurethane may be formed as a result of the curing reaction.

[0228] When constituting the two-component composition, the main agent parts may contain at least the curable component, catalyst, and curing rate regulator among the above-described components. Also, the curing agent parts may contain at least the curing agent (polyisocyanate). In the above cases, the main agent parts do not contain the curing agent (polyisocyanate), and the curing agent parts do not necessarily contain the curable component, catalyst, and curing regulator.

[0229] The filler component may be included in any one of the main agent and curing agent parts, or may be included in both the main agent and curing agent parts. When the filler component is entirely included in the main agent and curing agent parts, the same amount of the filler component may be included in the main agent and curing agent parts.

[0230] For example, in the above case, the upper limit of the ratio of the filler component in the main agent part may be about 95 wt%, 94.5 wt%, 94 wt%, 93.5 wt%, 93 wt%, 92.5 wt%, 92 wt%, 91.5 wt%, 91 wt%, 90.5 wt%, 90.0 wt%, 89.5 wt% or 89.0 wt%, and the lower limit thereof may be about 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, about 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt% or 88 wt%. The ratio may be within the range of any one of the lower limits described above to any one of the upper limits described above, or between any one of the lower limits described above and any one of the upper limits described above.

[0231] The ratio of the filler component in the main agent part can also be defined as the ratio to 100 parts by weight of the total weight of the curable component in the main agent part or the reactive compound present in the curable component. For example, the lower limit of the ratio of the filler component may be about 500 parts by weight, 550 parts by weight, 600 parts by weight, 650 parts by weight, 700 parts by weight, 750 parts by weight, 800 parts by weight, 850 parts by weight, 900 parts by weight, 950 parts by weight or 1,000 parts by weight, and the upper limit thereof may be about 2,000 parts by weight, 1,800 parts by weight, 1,600 parts by weight, 1,400 parts by weight, 1,200 parts by weight, 1,000 parts by weight, 950 parts by weight or 900 parts by weight. The ratio may be within the range of any one of the lower limits described above to any one of the upper limits described above, or between any one of the lower limits described above and any one of the upper limits described above.

[0232] In the above case, the upper limit of the proportion of the filler component in the hardener part may be about 95% by weight, 94.5% by weight, 94% by weight, 93.5% by weight, 93% by weight, 92.5% by weight, 92% by weight, 91.5% by weight, 91% by weight, 90.5% by weight, 90.0% by weight, 89.5% by weight or 89.0% by weight, and the lower limit thereof may be about 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, about 75% by weight, 76% by weight, 77% by weight, 78% by weight, 79% by weight, 80% by weight, 81% by weight, 82% by weight, 83% by weight, 84% by weight, 85% by weight, 86% by weight, 87% by weight or 88% by weight. The proportion may be within the range of not less than any one of the lower limits described above, not more than any one of the upper limits described above, or between any one of the lower limits described above and any one of the upper limits described above.

[0233] The proportion of the filler component in the hardener part can also be defined as the proportion with respect to 100 parts by weight of the hardener (polyisocyanate) of the hardener part. For example, the lower limit of the proportion of the filler component may be about 500 parts by weight, 550 parts by weight, 600 parts by weight, 650 parts by weight, 700 parts by weight, 750 parts by weight, 800 parts by weight, 850 parts by weight, 900 parts by weight, 950 parts by weight, 1,000 parts by weight, 1,500 parts by weight, 2,000 parts by weight or 2,500 parts by weight, and the upper limit thereof may be about 4,000 parts by weight, 3,500 parts by weight or 3,000 parts by weight. The proportion may be within the range of not less than any one of the lower limits described above, not more than any one of the upper limits described above, or between any one of the lower limits described above and any one of the upper limits described above.

[0234] Other components such as catalysts, plasticizers, flame retardants, etc. can be included in the main agent and / or hardener part as necessary.

[0235] In the two-component composition, the lower limit of the volume ratio (P / N) of the volume (P) of the main agent part to the volume (N) of the curing agent part may be 0.8, 0.85, 0.9, 0.95, or 1, and the upper limit may be 1.2, 1.15, 1.1, 1.05, or 1. The ratio (P / N) may be equal to or higher than any one of the aforementioned lower limits, equal to or lower than any one of the aforementioned upper limits, or within the range between any one of the aforementioned lower limits and any one of the aforementioned upper limits.

[0236] In one example, the two-component composition can be formulated such that when the main agent part and the curing agent part have the volume ratio, the aforementioned equivalent ratio (OH / NCO) can be ensured.

[0237] Such a two-component composition or its cured body can also exhibit the adhesive strength to aluminum and polyester, thermal conductivity, hardness, bending radius, insulation, flame retardancy, specific gravity, shrinkage rate, coefficient of thermal expansion, and / or the temperature of 5% weight loss in thermogravimetric analysis (TGA) described above.

[0238] The present invention also relates to a thermal interface material (TIM: Thermal Interface Material). The thermal interface material may be a cured body of the resin composition.

[0239] Therefore, the thermal interface material can also exhibit the adhesive strength to aluminum and polyester, thermal conductivity, hardness, bending radius, insulation, flame retardancy, specific gravity, shrinkage rate, coefficient of thermal expansion, and / or the temperature of 5% weight loss in thermogravimetric analysis (TGA) described above.

[0240] Therefore, the thermal interface material may contain components included in the resin composition or components derived from those components. For example, when the resin composition is a polyurethane composition, the thermal interface material may contain the polyurethane.

[0241] Polyurethane can be formed by the reaction of the above-described reactive compound and a curing agent (polyisocyanate). Therefore, the polyurethane may contain units derived from the reactive compound.

[0242] The present invention also relates to a product containing the resin composition or a cured product thereof (a thermal interface material or a heat transfer material). The resin composition or a cured product thereof of the present invention can be usefully applied as a heat dissipation material. Therefore, the product may contain a heat generating component. The term "heat generating component" means a component that generates heat during use, and its type is not particularly limited. Typical heat generating components include various electrical / electronic products including a battery cell, a battery module, or a battery pack.

[0243] The product of the present invention may include, for example, the heat generating component, and the resin composition (or the two-component composition) and a cured product thereof that are present adjacent to the heat generating component.

[0244] The specific method for constructing the product of the present invention is not particularly limited, and when the resin composition or two-component composition or a cured product thereof of the present invention is applied to a heat dissipation material, the product can be constructed in various known ways.

Advantages of the Invention

[0245] The present invention provides a curable composition, a thermal interface material (TIM: Thermal Interface Material), and uses thereof. In the present invention, the curable composition or the thermal interface material or the like can exhibit a high thermal conductivity while showing a low adhesive force to a predetermined adherend. Further, in the present invention, the low adhesive force can be achieved without using an adhesion adjusting component such as a plasticizer or while minimizing the use ratio thereof.

[0246] In the present invention, further, the curable composition can exhibit a precisely controlled curing rate and at the same time have excellent curability.

[0247] The present invention can also provide a product containing the curable composition, a cured product thereof, or a thermal interface material. [Brief description of the drawings]

[0248]

Figure 1

Figure 2

[0249] The present invention will now be described in detail with reference to examples, but the scope of the present invention is not limited to the following examples.

[0250] The cured products mentioned below are formed by mixing the base part and the curing part of the resin composition of the examples manufactured in a two-component type so as to satisfy the OH / NCO equivalent ratio described in each example, and then maintaining the mixture at room temperature (about 25°C) for about 24 hours.

[0251] In the present examples, the physical properties were evaluated by the following methods.

[0252] 1. Thermal Conductivity The thermal conductivity of the resin composition (curable composition) or its cured product was measured by the hot-disk method according to the ISO22007-2 standard. Specifically, a mixture of the base material part and the curing agent part of the examples or comparative examples in a volume ratio of 1:1 was placed in a mold with a thickness of about 7 mm, and the thermal conductivity was measured in the through-plane direction using a hot-disk device. As specified in the standard (ISO22007-2), the hot-disk device is a device that can confirm the thermal conductivity by measuring the temperature change (electrical resistance change) by heating a sensor with a double spiral structure of nickel wire, and the thermal conductivity was measured according to this standard.

[0253] 2. Measurement of adhesion to polyester The adhesion to polyester was evaluated for test pieces manufactured by attaching a PET (polyethylene terephthalate) film to an aluminum plate. As the PET film, a film with a width of about 10 mm and a length of about 200 mm was used, and as the aluminum plate, an aluminum plate with a width and length of 100 mm each was used. The resin composition was applied entirely on the surface of the aluminum plate, and the PET film was adhered on the resin composition and maintained at room temperature (about 25°C) for about 24 hours to produce test pieces. At this time, about 100 mm of the entire width and a length portion of the PET film were adhered to the aluminum plate via the resin composition. With the aluminum plate of the test piece fixed, the adhesion was measured while peeling the PET film from the aluminum plate in the length direction. For the adhesion, after applying the resin composition (a mixture of the main component part and the curing agent part at a volume ratio of 1:1) to the aluminum plate so that the thickness after curing was about 2 mm, the PET film was brought into close contact with the layer of the resin composition and maintained at room temperature (about 25°C) for about 24 hours to cure the resin composition. The peeling was carried out at a peeling speed of about 0.5 mm / min and a peeling angle of 180 degrees until the PET film was completely peeled off.

[0254] 3. Measurement of Adhesion to Aluminum An uncured resin composition (a mixture of the main component part and the curing agent part at a volume ratio of 1:1) was coated in the center of an aluminum substrate with horizontal and vertical lengths of 2 cm and 7 cm respectively so that the horizontal and vertical lengths were about 2 cm each. Further, an aluminum substrate with horizontal and vertical lengths of 2 cm and 7 cm respectively was adhered on the coating layer, and the resin composition was cured while maintaining that state. In the above, the two aluminum substrates were adhered at an angle of 90 degrees to each other. Then, with the upper aluminum substrate fixed, the lower aluminum substrate was pressed at a speed of 0.5 mm / min, and the force during the separation of the lower aluminum substrate was measured. The adhesion to aluminum was obtained by dividing the maximum value of the force measured in the process by the area of the test piece.

[0255] 4. Measurement of Hardness The hardness of the cured product of the resin composition was measured according to ASTM D 2240 and JIS K 6253 standards. It was carried out using an ASKER, durometer hardness instrument. An initial hardness was measured by applying a load of 1 kg or more (about 1.5 kg) to the surface of a flat sample (resin layer), and the hardness was evaluated by confirming the measured value stabilized after 15 seconds.

[0256] 5. Measurement of Curing Rate The curing rate of the resin composition was evaluated through the change in hardness over time. At this time, the hardness was measured according to ASTM D 2240 and JIS K 6253 standards, the same as described above.

[0257] The main agent part and the curing agent part were mixed at a volume ratio of 1:1, and while maintaining at room temperature (about 25°C), the change in hardness over time was confirmed immediately after mixing to measure the curing rate.

[0258] 6. Measurement of Bending Radius The bending radius of the cured product was evaluated using a cured product with a width, length, and thickness of 1 cm, 10 cm, and 2 mm, respectively. The bending radius is the minimum radius of the cylinder when the cured product is attached to a cylinder having various radii and bent along the longitudinal direction, and no crack occurs in the cured product.

[0259] 7. Measurement of Loading Rate The loading rate (kgf) of the resin composition was evaluated using an apparatus as shown in Figure 1. The apparatus in Figure 1 is an apparatus 1 in which two cartridges 2, 2a, 2b and one static mixer 5 are connected.

[0260] In the said apparatus 1, as the cartridges 2, 2a, 2b, a cartridge (Sulzer, AB050 - 01 - 10 - 01) was used, where the material injection part is circular with a diameter of 18 mm, the material discharge parts 4, 4a, 4b are circular with a diameter of 3 mm, the height is 100 mm, and the internal volume is 25 ml. As the static mixer 5, a stepped - type static mixer (Sulzer, MBH - 06 - 16T) was used, where the discharge part 7 is circular with a diameter of 2 mm and the number of elements is 16.

[0261] As the pressurizing means 3, 3a, 3b of the said apparatus (means for extruding the composition loaded in the cartridge), a TA (Texture analyzer) was used.

[0262] The loading rate was measured as follows: After loading the main agent part into one of the two cartridges 2a, 2b and the curing agent part into the other cartridge, a constant force was applied by the pressurizing means 3, 3a, 3b so that the main agent and the curing agent parts were mixed by the static mixer 5 via the first discharge parts 4a, 4b and then discharged from the second discharge part 7.

[0263] The main agent and the curing agent parts loaded into the two cartridges 2a, 2b were pressurized at a constant speed of 1 mm / s by TA (Texture analyzer) 3a, 3b and injected into the static mixer 5. From the time when the main agent and the curing agent parts injected into the mixer 5 were mixed in the mixer 5 and first discharged from the discharge part 7, while measuring the force applied to the pressurizing means, the maximum value of the force at the point where the force reached the maximum value was taken as the loading rate. When measuring the force applied to the TA in the above - mentioned manner, usually, the force first continuously increases and then decreases, or the increasing force shows a tendency not to increase further. The loading rate is the maximum force before the decrease or the maximum force at the point where it does not increase further.

[0264] 8. Measurement of average particle size The average particle size of the filler is the D50 particle size of the filler, which is the particle size measured by a Malvern MASTERSIZER 3000 device in accordance with the ISO-13320 standard. Ethanol was used as the solvent during the measurement. The laser incident on the filler dispersed in the solvent is scattered, and the intensity and directionality values of the scattered laser vary depending on the size of the filler. By analyzing this using Mie theory, the D50 particle size can be determined. The distribution is obtained by converting it to the diameter of a sphere having the same volume as the filler dispersed through the analysis, thereby obtaining the D50 value, which is the median of the distribution, and the particle size can be evaluated.

[0265] 9. Evaluation of Module Workability A resin composition (a mixture of the main agent and the curing agent parts at a volume ratio of 1:1) was applied to an aluminum plate in the shape of a square with sides of 8 cm each in the horizontal and vertical directions and a thickness of about 2 mm, and cured by maintaining it at normal temperature (about 25 °C) and normal humidity (about 40% relative humidity) for about 24 hours. Next, while peeling the cured product from the aluminum plate, the module workability was evaluated according to the following criteria.

[0266] <Evaluation Criteria> ○: When the cured product of the resin composition peels off in a sheet form without leaving any residue on the aluminum plate ×: When it is impossible to peel the cured product of the resin composition from the aluminum plate, or when residues remain even after peeling

[0267] 10. Evaluation of Mixing State The mixing state was measured using an apparatus similar to that for measuring the load rate (kgf). After loading the main agent part into one of the two cartridges 2a and 2b of the apparatus and loading the curing agent part into the other one, a constant force was applied by the pressurizing means 3, 3a, and 3b, and the state of the mixture (a mixture with a 1:1 volume ratio of the main agent part and the curing agent part) when it was discharged from the static mixer 5 via the first discharge parts 4a and 4b and then discharged to the second discharge part 7 was visually observed, and the mixing state was evaluated based on the following criteria. When evaluating the mixing state, dyes were added to the main agent part and the curing agent part respectively so that they had different colors from each other.

[0268] <Evaluation criteria> ○: When the color of the mixture of the main agent part and the curing agent part is observed to be uniformly mixed ×: When the color of the mixture of the main agent part and the curing agent part is not uniformly mixed and marbling or the like is observed

[0269] 11. Measurement of weight average molecular weight The weight average molecular weight (Mw) was measured using GPC (Gel permeation chromatography). Specifically, for the weight average molecular weight (Mw), the sample to be analyzed was put into a 5 mL vial, diluted with a THF (tetrahydrofuran) solvent to a concentration of about 1 mg / mL, and then the calibration standard sample and the analysis sample were filtered through a syringe filter (pore size: 0.45 μm) and measured. As the analysis program, ChemStation of Agilent technologies was used, and the weight average molecular weight (Mw) could be obtained by comparing the elution time of the sample with the calibration curve.

[0270] <GPC measurement conditions> Equipment: 1200 series of Agilent technologies Column: Using TL Mix.A&B of Agilent technologies Solvent: THF (tetrahydrofuran) Column temperature: 35 °C Sample concentration: 1 mg / mL, 200 μl injection Standard sample: Using polystyrene (MP: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

[0271] Production Example 1. The oil-modified polyol compound (reactive compound) of the following Chemical Formula A was produced in the following manner.

[0272]

Chemical formula

[0273] In Chemical Formula A, n and m are each greater than 0, and their sum (n + m) is about 4.8.

[0274] Polycaprolactone polyol (Perstorp, Capa 3031) and isononanoic acid, a saturated fatty acid, were mixed at a weight ratio of 1:0.53 (Capa 3031: isononanoic acid). Next, a catalyst (Tin(II) 2-ethylhexanoate (Sigma-Aldrich)) was added at 0.1 part by weight per 100 parts by weight of the mixture, and the mixture was maintained while stirring at 150 °C for 30 minutes under an inert gas purge condition. Next, a small amount of xylene, an azeotropic solution, was added, the temperature was raised to 200 °C, and after reacting for 3 hours or more, the pressure was reduced to 80 Torr or less to remove xylene and unreacted substances. After cooling the reaction product, it was filtered to obtain the target product (compound of Chemical Formula A).

[0275] As a result of GPC analysis performed on the target product, the weight average molecular weight was at a level of about 876 g / mol. Figure 2 is a diagram showing the results of GPC analysis performed on the target product.

[0276] Example 1. Manufacture of the main agent parts The oil-modified polyol compound of Production Example 1, a general polyol compound (Kuraray, F-2010), a urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), a carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), a filler component, and a plasticizer (diisononyl adipate) were mixed at a weight ratio of 90:10:0.63:0.86:1054:14.5 (Production Example 1:F-2010:DBTDL:2-EHA:filler:plasticizer) to manufacture the main agent parts. As the filler component, a first alumina filler with an average particle size of about 70 μm, a second alumina filler with an average particle size of about 20 μm, a third alumina filler with an average particle size of about 1 μm, and aluminum hydroxide (ATH, Aluminium trihydroxide) with an average particle size of about 1 μm were mixed at a weight ratio of 62.5:21:10:6.5 (first alumina:second alumina:third alumina:ATH) for production.

[0277] Manufacture of the curing agent parts Polyisocyanate (Vencorex, Tolonate HDT-LV2) was used as the curing agent. The polyisocyanate, a filler component, and a plasticizer (diisononyl adipate) were mixed at a weight ratio of 100:2516:119 (polyisocyanate:filler:plasticizer) to manufacture the main agent parts. As the filler component, the same components as those of the main agent parts were used.

[0278] The curing agent parts were manufactured such that when the curing agent parts were blended with the main agent parts at a volume ratio of 1:1, the equivalent ratio (OH / NCO) of the hydroxy groups (OH) present in the main agent parts and the isocyanate groups (NCO) present in the curing agent parts was about 170.

[0279] Manufacture of the resin composition and the cured body The main agent and the curing agent parts were each prepared to produce a resin composition (curable composition). After mixing the main agent and the curing agent parts at a volume ratio of approximately 1:1, they were maintained at room temperature (about 25°C) to form a cured body.

[0280] Example 2. The main agent part was produced in the same manner as in Example 1, except that the blending ratio was changed to 90:10:0.63:1.26:1054:14.5 (Production Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer) during the production of the main agent part. The curing agent part, the resin composition, and the cured body were produced in the same manner as in Example 1.

[0281] Example 3. The main agent part was produced in the same manner as in Example 1, except that the blending ratio was changed to 90:10:0.63:2.52:1054:14.5 (Production Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer) during the production of the main agent part. The curing agent part, the resin composition, and the cured body were produced in the same manner as in Example 1.

[0282] Example 4. The main agent part was produced in the same manner as in Example 1, except that the blending ratio was changed to 90:10:0.63:3.78:1054:14.5 (Production Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer) during the production of the main agent part. The curing agent part, the resin composition, and the cured body were produced in the same manner as in Example 1.

[0283] Example 5. The main agent part was produced in the same manner as in Example 1, except that the blending ratio was changed to 90:10:0.23:0.69:1054:14.5 (Production Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer) during the production of the main agent part. The curing agent part, the resin composition, and the cured body were produced in the same manner as in Example 1.

[0284] Example 6. The main component parts were produced in the same manner as in Example 1, except that the compounding ratio was changed to 90:10:0.34:1.72:1055:14.7 (Production Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer) during the production of the main component parts. The curing agent parts, resin composition, and cured body were produced in the same manner as in Example 1.

[0285] Example 7. The main component parts were produced in the same manner as in Example 1, except that the compounding ratio was changed to 90:10:0.57:2.86:1054:14.5 (Production Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer) during the production of the main component parts. The curing agent parts, resin composition, and cured body were produced in the same manner as in Example 1.

[0286] Comparative Example 1. The main component parts were produced in the same manner as in Example 1, except that the carboxylic acid compound (2-EHA, 2-ethylhexanoic acid) was not used and the compounding ratio was changed to 90:10:0.23:1054:14.5 (Production Example 1: F-2010: DBTDL: filler: plasticizer) during the production of the main component parts. The curing agent parts, resin composition, and cured body were produced in the same manner as in Example 1.

[0287] The physical property evaluation results sorted for each of the above Examples and Comparative Examples are as shown in Table 1 below. In Table 1 below, the hardness is the hardness measured after maintaining a 1:1 volume ratio mixture of the main component parts and the curing agent parts at room temperature (about 25°C) for 24 hours.

[0288] In Table 1 below, Adhesion 2 is the adhesion to the polyester, and Adhesion 1 is the adhesion to the aluminum.

[0289]

Table 1

[0290] The results of evaluating the curing rate of the resin compositions of the above Examples and Comparative Examples were sorted and described in Table 2 below.

[0291] The curing rate was evaluated by measuring the hardness over time while maintaining a 1:1 volume ratio mixture of the main agent part and the curing agent part at room temperature (about 25°C). In Table 2 below, H represents time. That is, 1H is the hardness at the time when 1 hour has passed after the mixing.

[0292]

Table 2

[0293] From the results of Table 1 and Table 2, it can be confirmed that in the resin composition of the example, the curing reaction is delayed after the main agent part and the curing agent part are blended due to the presence of the carboxylic acid compound.

[0294] Specifically, in the case of the example, the time point for confirming the hardness after blending is at least 2.5 hours or more, and the hardness at the first confirmation is not high. On the other hand, in the case of Comparative Example 1, a high hardness is confirmed immediately after blending, indicating that rapid curing occurs.

[0295] Looking at the results of Table 1, it can be seen that even when there is a delay in the curing reaction as described above, the target physical properties (such as thermal conductivity, low adhesion, and flexibility) are also ensured for the final cured body.

[0296] However, in the case of Comparative Example 1, a high hardness is confirmed before 2 hours have passed after the main agent part and the curing agent part are blended, indicating that no delay in curing is induced.

Claims

1. A curable composition comprising a curable component containing a reactive compound having a hydroxy group, a carboxylic acid compound, a urethane reaction catalyst and a filler component.

2. The curable composition according to claim 1, wherein the curable component contains a first reactive compound having one hydroxy group and a second reactive compound having two or more hydroxy groups.

3. The curable composition according to claim 2, wherein the second reactive compound having two or more hydroxy groups contains a third reactive compound having two hydroxy groups and a fourth reactive compound having three or more hydroxy groups.

4. The curable composition according to claim 1, wherein the reactive compound contains a branched hydrocarbon chain having 5 or more carbon atoms at the terminal.

5. The curable composition according to claim 3, wherein the first reactive compound and the third reactive compound each contain a branched hydrocarbon chain having 5 or more carbon atoms at the terminal.

6. The curable composition according to claim 3, wherein the fourth reactive compound contains a polycaprolactone polyol unit or an alkanediol unit; a polyol unit and a dicarboxylic acid unit.

7. The curable composition according to claim 1, wherein the carboxylic acid compound is a monofunctional compound having a hydrocarbon group.

8. The curable composition according to claim 7, wherein the monofunctional compound has a molecular weight in the range of 50 to 400 g / mol.

9. The curable composition according to claim 1, wherein the carboxylic acid compound has a pKa in the range of 2 to 9.

10. The curable composition according to claim 1, wherein the carboxylic acid compound is contained in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the curable component.

11. The curable composition according to claim 1, wherein the urethane reaction catalyst is a tin catalyst.

12. The curable composition according to claim 1, wherein the urethane reaction catalyst is contained in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the curable component.

13. The curable composition according to claim 1, wherein the weight ratio of the carboxylic acid compound to the urethane reaction catalyst is 1 or more.

14. The curable composition according to claim 1, which forms a cured body having a thermal conductivity of 2.0 W / mk or more.

15. The adhesive strength to aluminum is 0.15 N / mm ２ The curable composition according to claim 1, which forms the following cured product.

16. The curable composition according to claim 1, which forms a cured body having an adhesive force to polyester of 100 gf / cm or less.

17. The curable composition according to claim 1, which forms a cured body having a Shore OO hardness of 95 or less.

18. The curable composition according to claim 1, further comprising a plasticizer.

19. The curable composition according to claim 1, comprising 500 parts by weight or more of the filler component with respect to 100 parts by weight of the curable component.

20. A two-component composition comprising a main agent part and a curing agent part, wherein the main agent part is the curable composition according to any one of claims 1 to 19.

21. The two-component composition according to claim 20, wherein the curing agent part comprises a polyisocyanate compound and a filler component.

22. Comprising a heating element and a heat conductive material present adjacent to the heating element, wherein the heat conductive material comprises a cured body of the curable composition according to claim 1 or the two-component composition according to claim 20.

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