Hardening composition

Abstract

The present application provides a curable composition, a thermal interface material (TIM), and uses thereof. In the present application, the curable composition or the thermal interface material, etc., can exhibit a low adhesive force to a predetermined adherend while showing a high thermal conductivity. Further, in the present application, 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 application, further, the curable composition can exhibit a precisely controlled curing rate and at the same time have excellent curability. In the present application, 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 Nos. 10-2022-0116476 and 10-2022-0116475 filed on September 15, 2022, and all the contents disclosed in the documents of the Korean patent applications are included as part of this specification. This application relates to a curable composition, a thermal interface material (TIM), and uses thereof.

Background Art

[0002] 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). As the resin binder in the heat dissipation material as described above, usually, a silicone resin, a polyolefin resin, an acrylic resin, an epoxy resin, or the like is used.

[0003] A heat dissipation material is basically 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 adhesion to a specific adherend while having high thermal conductivity. 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 during the process, the heat dissipation material needs to exhibit low adhesion.

[0004] Among the known heat dissipation materials, a material that exhibits low adhesion is a material in which a silicone resin is applied as a resin binder. However, silicone resins are relatively expensive. In addition, since silicone resins contain components that cause poor contact when applied to electronic / electrical products, their applications are limited.

[0005] The polyurethane material 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. 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 use. In addition, for a heat dissipation material having curability, it is necessary to control the curing rate of the heat dissipation material.

[0006] That is, when forming a heat dissipation material using a heat dissipation material having curability, a step of applying the heat dissipation material before curing to a target position and then 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, since the viscosity and hardness of the material also rapidly increase, there is a problem that the time during which the said replacement or position change is possible becomes very short.

[0007] 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, the said waiting time cannot be appropriately ensured.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present application aims to provide a curable composition, 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 application is to enable the curable composition or the thermal interface material, etc., to exhibit high thermal conductivity while showing low adhesive force to a predetermined adherend. Further, the object of the present application includes achieving the low adhesive force without using an adhesion-regulating component such as a plasticizer or minimizing its usage ratio.

[0010] The present application also aims to enable the curable composition to exhibit a precisely controlled curing rate and excellent curability at the same time. The present application also aims to provide a product including the curable composition, its cured product, or the thermal interface material.

Means for Solving the Problems

[0011] 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 normal temperature. The term "normal 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.

[0012] Among the physical properties mentioned in this specification, when the measurement pressure affects the result, unless otherwise specified, the physical property is the physical property measured at normal pressure. The term "normal pressure" is the natural pressure without pressurization and depressurization, and usually, the atmospheric pressure within the range of about 700 mmHg to 800 mmHg is referred to as normal pressure.

[0013] This application 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 that can form 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 that can form resins through a curing and / or polymerization reaction.

[0014] The resin composition may be a curable composition. The curable composition can be cured to form a thermal interface material (TIM). Therefore, in this specification, the cured body of the resin composition and the thermal interface material can refer to the same object.

[0015] When the resin composition of this application 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 the 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 the curing are physically separated and contained separately.

[0016] When the resin composition of this application is a curable composition, the resin composition may be a room temperature curing type, a heat curing type, an energy ray curing type, and / or a moisture curing type. The term room temperature curing type refers to a resin composition in which the curing reaction can start and / or proceed at room temperature, the term heat curing type refers to a resin composition in which the curing reaction can start and / or proceed by the application of heat, the term energy ray curing type refers to a resin composition in which the curing reaction can start and / or proceed by the irradiation of energy rays (for example, ultraviolet rays, electron beams, etc.), and the term moisture curing type refers to a resin composition in which the curing reaction can start and / or proceed in the presence of moisture.

[0017] The resin composition of this application may be a solvent type or a solvent-free type. Considering the viewpoints of application efficiency and environmental load, etc., it is appropriate to be a solvent-free type.

[0018] The resin composition of the present application 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 thermal interface material which is a cured body of the resin composition may contain the polyurethane. In one exemplary case, the polyurethane can be formed by the reaction of a curable component described later and its curing agent.

[0019] The resin composition of the present application can exhibit a low adhesive force to a specific adherend or can form a cured body 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 applying such a component as a plasticizer, the adhesive force of the polyurethane material can be reduced, but problems 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 may occur. However, in the present application, 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 application, 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.

[0020] The adhesive force of the resin composition or its cured body to aluminum may be 1 N / mm 2 or less. In other exemplary cases, the upper limit of the adhesive force of the resin composition or its cured body to aluminum is 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 2 may also be used. The adhesive strength of the resin composition or its cured product to aluminum may be less than or equal to any one of the upper limits described above. In the present application, the lower limit of the adhesive strength to aluminum is not particularly limited. In one example, the adhesive strength to aluminum is 0 N / mm 2 or more or exceeds 0 N / mm 2 may also be used. The resin composition may be a resin composition whose adhesive strength to aluminum is substantially not measurable, or a resin composition capable of forming a cured product whose adhesive strength is substantially not measurable. Therefore, the adhesive strength to aluminum may be 0 N / mm 2 or more or exceeds 0 N / mm 2 and less than or equal to any one of the upper limits described above. The adhesive strength of the resin composition or its cured product to aluminum can be measured by the method described in the examples of this specification.

[0021] The resin composition or its cured product may have an adhesive force to polyester of 100 gf / cm or less. In other examples, the upper limit of the adhesive force 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 force of the resin composition or its cured product to polyester may be equal to or less than any one of the above-mentioned upper limits. In the present application, the lower limit of the adhesive force to polyester is not particularly limited. In one example, the lower limit of the adhesive force 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 or 20 gf / cm. The resin composition or its cured product may not substantially exhibit an adhesive force to polyester. The adhesive force of the resin composition or its cured product to polyester may be in the range between any one of the above-mentioned lower limits and any one of the above-mentioned upper limits. The adhesive force of the resin composition or its cured product to polyester can be measured in the manner described in the examples of this specification.

[0022] 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 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 more, or about 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 upper limit of the thermal conductivity of the resin composition or its cured product may be 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 within 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 later.

[0023] 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 extremely 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, 95 or 80. 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 later.

[0024] 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 below any one of the upper limits described above. The lower limit of the bending radius may be, for example, about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. The bending radius may be above any one of the lower limits described above. The bending radius may be within the range between any one of the upper limits described above and any one of the lower limits described above. 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.

[0025] The resin composition of the present application 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 measured in accordance with ASTM D149 of the resin composition or its cured product 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.

[0026] 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). Thereby, it is possible to ensure stability against fires and other accidents that are a concern according to the application of the resin composition.

[0027] 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 enable the resin composition or its cured product to 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 originally, or a filler with surface treatment can be applied, or a method such as this can be used.

[0028] The resin composition may have a low shrinkage rate during or after the curing process. Through this, it is possible to prevent peeling, generation of voids, 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, and may be, for example, 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.

[0029] The resin composition or its cured product may have a low coefficient of thermal expansion (CTE). Through this, it is possible to prevent peeling, generation of 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.

[0030] 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 residue at 800 °C of 70% by weight or higher. Such properties can further improve the high-temperature stability. In other examples, the residue 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 residue 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 adjustment of the composition of the resin composition. For example, the residue 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 residue increases.

[0031] The resin composition of the present application 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.

[0032] 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. 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.

[0033] 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 is 1 confirmable 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.

[0034] 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 terminal. Therefore, a reactive compound that does not contain a linear or branched hydrocarbon group with 3 or more carbon atoms at its terminal 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 to 5 ppm in 1H NMR. By applying the oil-modified compound, it is possible to ensure a low adhesive force to a specific material while being formed of a polyurethane material and not using an adhesion-reducing component such as a plasticizer or minimizing its usage amount.

[0035] The lower limit of the number of carbon atoms of the linear or branched hydrocarbon group contained at the terminal 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 lower limits described above. 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 upper limits described above. The number of carbon atoms may be within the range between any one of the lower limits described above and any one of the upper limits described above.

[0036] 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.

[0037] 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 any one of the upper limits of the number of carbon atoms of the linear or branched hydrocarbon group described above 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.

[0038] 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 is no particular limitation on the type of the substituent. For example, a halogen atom such as fluorine can be exemplified as the substituent.

[0039] In one example, the hydrocarbon group may be included in the substituent of the following Chemical Formula 1.

Chemical formula

[0040] 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 equal to or more than any one of the lower limits described above, equal to or less 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.

[0041] The oil-modified compound can have various forms as long as it contains the hydroxy group and the hydrocarbon group. 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 the alkane, the alkene or the alkyne may be, for example, 1 to 20, 1 to 16, 1 to 8 or 4 to 6. Such a hydrocarbon compound 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 on the same carbon atom or on other carbon atoms in the alkane, the alkene or the alkyne.

[0042] In another example, the reactive compound may be a compound having a polyester skeleton or a polyether skeleton. In such a case, the reactive compound may be an oligomeric compound or a polymeric compound. In one example, when the reactive compound having the polyester skeleton is a polyol compound, the compound is a so-called polyester polyol, and it may be a polyol having a structure in which the hydrocarbon group is linked to such a polyester polyol.

[0043] Also, when the reactive compound having the polyether skeleton is a polyol compound, the compound is a so-called polyether polyol, and it may be a polyol having a structure in which the hydrocarbon group is linked to such a polyether polyol. In one example, the polyester skeleton may be a so-called polycaprolactone skeleton, and the polyether skeleton may be a so-called polyalkylene skeleton.

[0044] In one example, the polyester skeleton may be a skeleton having a repeating unit represented by the following Chemical Formula 2.

Chemical Formula

[0045] In this specification, the alkylene group and the alkylidene group both mean divalent substituents 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 distinguished from each other in this respect.

[0046] 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. 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 lower limits described above, equal to or less 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.

[0047] The backbone of Chemical Formula 2 may be a so-called carboxylic acid polyol backbone or a caprolactone polyol backbone. Such a backbone can be formed by known methods. For example, the carboxylic acid polyol backbone can be formed by reacting a component containing a carboxylic acid and a polyol (e.g., diol or triol, etc.), and the caprolactone polyol backbone can be formed by reacting a component containing caprolactone and a polyol (e.g., diol or triol, etc.). The carboxylic acid may be a dicarboxylic acid. In the oil-modified compound having the backbone of Chemical Formula 2, the hydroxy group or the hydrocarbon group described above may be present at the end of the backbone of Chemical Formula 2.

[0048] In such a case, the backbone of Chemical Formula 2 can be represented by the following Chemical Formula 3.

Chemical Formula

Chemical Formula

[0049] In the oil-modified compound, the lower limit of the number of skeletons of 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 skeletons 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 oil-modified compound having the polyester skeleton may have a linear or branched structure.

[0050] In the above, the linear structure is a structure in which a main chain containing the skeleton of 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 Chemical Formula 2 or 3 is bonded as a side chain to the main chain containing the skeleton of Chemical Formula 2 or 3. In the above, the number of chains containing the skeleton of Chemical Formula 2 or 3 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.

[0051] In one example, the oil-modified compound having the polyester skeleton may be a compound in which at least a part of the hydrogen atoms of a hydrocarbon compound such as an alkane, alkene or alkyne is substituted with the hydroxy group and / or the skeleton of Chemical Formula 3. The number of carbon atoms of the hydrocarbon compound such as the alkane, alkene or alkyne may be, for example, 1 to 20, 1 to 16, 1 to 8 or 4 to 6.

[0052] Such a hydrocarbon compound such as an alkane, alkene or alkyne may be linear, branched or cyclic. Further, the hydroxy group and / or the skeleton of Chemical Formula 3 may be substituted on the same carbon atom in the alkane, alkene or alkyne, or may be substituted on other carbon atoms.

[0053] In one example, the polyether skeleton may be a skeleton having a repeating unit represented by the following Chemical Formula 5.

[0054]

Chemical Formula

[0055] In Chemical Formula 5, m is an arbitrary number indicating the number of repeating units, and may be, for example, a number in the range of 1 to 25. In the oil-modified compound having the skeleton of Chemical Formula 5, the hydroxy group or the hydrocarbon group described above may be present at the terminal of the skeleton of Chemical Formula 5. In such a case, the skeleton of Chemical Formula 5 may be represented by the following Chemical Formula 6.

Chem.

Chem.

[0056] 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 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. The polyol compound having the polyether skeleton can have a linear or branched structure.

[0057] 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, and the branched structure may be a form in which a side chain is linked to the main chain containing the skeleton of Chemical Formula 5 or 6 and a chain containing the skeleton of Chemical Formula 5 or 6 is also bonded. 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.

[0058] 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 are substituted with a hydroxy group and / or the skeleton of 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.

[0059] Such hydrocarbon compounds such as alkanes, alkenes or alkynes may be linear, branched or cyclic. Also, the hydroxy group and / or the skeleton of Formula 5 may be substituted on the same carbon atom in the alkane, alkene or alkyne, or may be substituted on other carbon atoms.

[0060] When the above-described oil-modified compound is an oligomeric or polymeric compound, the compound can have an appropriate level of molecular weight. 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 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.

[0061] By applying the oil-modified compound as described above, the desired physical properties can be more effectively ensured.

[0062] 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% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, or 85% by weight, and the upper limit may be about 95% by weight or 90% by weight. The proportion may be 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 within the range between any one of the lower limits described above and any one of the upper limits described above.

[0063] When the resin composition is a one-component type, the content of the oil-modified compound is the content within the one-component composition. When it is a two-component type composition, it is the content within the part where the oil-modified compound is present. For example, when the two-component type composition includes a physically separated main agent part and a curing agent part, and the oil-modified compound is included in the main agent part, the content of the oil-modified compound may be the content based on the total weight of the main agent part. Also, 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.

[0064] In other examples, 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, or 12 parts by weight. The proportion may be 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 within the range between any one of the lower limits described above and any one of the upper limits described above.

[0065] The ratio to the filler component is the ratio to 100 parts by weight of the total filler component contained in the resin composition when the resin composition is a one-component type, and is 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 when the resin composition is a two-component type.

[0066] The oil-modified compound can be synthesized through known synthesis 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, and 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. can be exemplified, but it is not limited thereto.

[0067] Also, there are no special restrictions on the type of polyol or alcohol compound that reacts with the saturated or unsaturated fatty acid. For example, an appropriate type among the general reactive compounds described later can be applied, but it is not limited thereto.

[0068] 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.

[0069] 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 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 non-oil-modified compound may also be a monomolecular, oligomeric, or polymeric compound.

[0070] The non-oil-modified compound can have various forms. 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.

[0071] In one example, the polyester polyol may be a skeleton having a repeating unit represented by the following Chemical Formula 8.

Chemical Formula

[0072] When the polyester polyol is a polycaprolactone polyol, L3 in Chemical Formula 8 may be a linear alkylene group having 5 carbon atoms. 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.

[0073] 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.

[0074] 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.

[0075] 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. The polyol compound having the polyester skeleton may have a linear or branched structure.

[0076] In the above, the linear structure is a structure in which the main chain containing the skeleton of Chemical Formula 8 exists and no other polymer chains are 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.

[0077] 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 polycarbodiimides 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.

[0078] 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.

[0079] The curable component of the curable composition of the present application 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. In one example, the curable component may include, among the reactive compounds described above, a monofunctional compound (also referred to as the first reactive compound) and a polyfunctional compound (also referred to as the second reactive compound). At this time, the monofunctional compound and the polyfunctional compound may each independently be the oil-modified compound or the non-oil-modified compound.

[0080] 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 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.

[0081] In the above case, the curable component may include, as the second reactive compound, 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). 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 three or more and may be less than or equal to any one of the upper limits described above.

[0082] 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.

[0083] The first to fourth reactive compounds may each independently be the oil-modified compound described above or a non-oil-modified compound.

[0084] 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.

[0085] 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 above-described polycaprolactone polyol unit or alkane diol unit; a compound containing a polyol unit and a dicarboxylic acid unit can be used. The resin composition may further contain, as an additional component, for example, a curing agent that reacts with the curable component.

[0086] As the curing agent, various types can be applied. However, in the case of a polyurethane composition which 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 between any one of the lower limits described above and any one of the upper limits described above.

[0087] The type of polyisocyanate used as the curing agent is not particularly limited, but in order to ensure the desired physical properties, a non-aromatic polyisocyanate containing no aromatic group can be used.

[0088] Also, if necessary, as the polyisocyanate, a bifunctional polyisocyanate and a polyisocyanate having three or more functional groups can be applied together. In the above, bifunctional means that the compound contains two isocyanate groups, and trifunctional means that the compound contains three or more isocyanate groups.

[0089] Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene 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(isocyanatomethyl) cyclohexane diisocyanate or dicyclohexylmethane diisocyanate; or carbodiimide-modified polyisocyanates, isocyanurate-modified polyisocyanates, etc. of any one or more of the above can be used. Further, as the polyisocyanate, an addition reaction product of the above-described diisocyanate and a polyol (e.g., trimethylolpropane, etc.) can also be used. Further, a mixture of two or more of the listed compounds can be used.

[0090] 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. 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.

[0091] The method for calculating the equivalent ratio (OH / NCO) is known. 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.

[0092]

Equation

[0093]

Number

[0094]

Number

[0095] In general formula 3, W NCO is the weight ratio of the polyisocyanate present in the hardener parts, and NCO % is the ratio of the isocyanate groups contained in the polyisocyanate having the weight ratio of the said W NCO is the ratio of the isocyanate groups contained in the polyisocyanate having the weight ratio of the said W In the above, W OH is the weight% (based on the total weight of the main agent parts) of each reactive compound present in the main agent parts, and the OH% of the said 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 groups by 100 after dividing by the molar mass of the single reactive compound.

[0096] In the above, W NCO is the weight% (based on the total weight of the hardener parts) of each polyisocyanate present in the hardener parts, and the NCO %is the percentage of the NCO period contained in 1 mol of each polyisocyanate, and is obtained by dividing the product of the number of moles of NCO groups contained in the single polyisocyanate and the molar mass of the NCO groups by the molar mass of the single polyisocyanate and then multiplying by 100. In General Formula 1, the dalton mass is a constant.

[0097] 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 a 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.

[0098] The resin composition may further contain a filler component. The term filler component means a component composed of a filler, that is, a component containing only a filler.

[0099] In one example, the filler component may contain two or more fillers having different average particle diameters from each other. In one example, the filler component may contain three or more fillers having different average particle diameters from each other, or may be composed of three to six, three to five, three to four or three fillers having different average particle diameters from each other. That is, in one example, the filler component can also contain only the three to six, three to five, three to four or three fillers having different average particle diameters from each other.

[0100] In other examples, the filler component can exhibit at least two peaks in the volume curve of the particle size distribution measured using laser diffraction. In one example, the filler component can exhibit three or more peaks, or three to six, three to five, three to four, or three peaks in the volume curve of the particle size distribution. For example, the range of filler components showing three peaks does not include filler components showing one, two, or four or more peaks.

[0101] The average particle size of the filler in this application means the particle size at which the volume cumulative is 50% in the volume curve of the particle size distribution measured by laser diffraction, which is also called the median diameter. That is, in this application, 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.

[0102] Therefore, 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.

[0103] Generally, when mixing two or more fillers with different average particle sizes to form a filler component, in the volume curve of the particle size distribution measured using laser diffraction for the filler component, peaks corresponding to the types of the mixed fillers appear. Therefore, for example, when three fillers with different average particle sizes are mixed to form a filler component, the volume curve of the particle size distribution measured using laser diffraction for the filler component shows three peaks.

[0104] The filler component of the resin composition of the present application may be a heat-conductive filler component. The term heat-conductive filler component means a filler component that functions such that the resin composition or its cured product exhibits the heat conductivity described above. In one exemplary embodiment, the filler component may include a first filler having an average particle size of at least 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.

[0105] In other examples, the first filler has 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.

[0106] In other examples, the second filler has 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.

[0107] 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 may be 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.

[0108] 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. 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.

[0109] 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.

[0110] 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 in 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.

[0111] 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 within the range described above, and can further satisfy the insulation property and the like described above through the application of the ceramic filler.

[0112] 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 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.

[0113] The lower limit of the ratio of the filler component to the total weight of 100 parts by 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 or 850 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 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.

[0114] When the resin composition is a one-component composition, the content of the filler component is a ratio based on the total weight of the resin composition. When the resin composition is a two-component resin composition, the content of the filler component may be a ratio based on the total weight of the main agent part and the curing agent part of the two-component composition, or may be a ratio based on the total weight of the main agent or the curing agent part alone.

[0115] 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 in substantially the same amount and introduce it into each of the main agent and the curing agent parts. In addition to the heat conductive filler, the filler component may contain various types of fillers as necessary. For example, carbon fillers such as graphite and fumed silica or clay can also be applied.

[0116] In addition to the components described above, the resin composition may further contain necessary components. In one example, the resin composition may further contain a plasticizer. As described above, in the present application, a low adhesive force can be ensured for a specific material without applying a plasticizer. However, a small amount of plasticizer can also be applied if necessary.

[0117] There are no special restrictions on the types of applicable plasticizers. For example, phthalate plasticizers such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), diisononyl phthalate (DINP), or polyethylene terephthalate (PET), adipate plasticizers such as dioctyl adipate (DOA) or diisononyl adipate (DINA), fatty acid plasticizers, phosphate plasticizers, or polyester plasticizers can be applied.

[0118] When a plasticizer is included, its ratio can be adjusted according to the purpose. For example, the lower limit of the ratio of the plasticizer to the total weight of 100 parts by 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, or 6.5 parts by weight, and the upper limit may be 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, 12 parts by weight, 11 parts by weight, 10 parts by weight, 9 parts by weight, 8 parts by weight, or 7 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 upper limits and any one of the above-mentioned lower limits. The ratio can also be changed in consideration of the composition of the entire resin composition and the intended use.

[0119] 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. As the urethane reaction catalyst, known components can be used without particular limitation, and examples thereof include organic catalysts such as tertiary amines and organometallic catalysts. From the viewpoint of exerting appropriate effects through combination with a curing rate retarder described later, an organometallic catalyst can be applied as the catalyst, and for example, a tin catalyst such as an organotin catalyst can be used.

[0120] 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 0.05 part by weight. The ratio may be within the range of any one of the lower limits described above or 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.

[0121] The resin composition may contain a curing rate regulator to ensure an appropriate curing rate. In the present application, 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 absent. Usually, the curing of the resin composition begins 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 curable type and a two-component type containing a main agent part and a curing agent part, the resin composition begins to cure when the main agent and the curing agent parts are mixed at room temperature.

[0122] 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.

[0123] Therefore, in the present application, 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 at this time. For example, a component that can react competitively or show an affinity with the curable components and catalysts contained in the resin composition and exhibit an effect of adjusting the curing rate can be applied.

[0124] 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.

[0125] As the thiol compound, for example, the compound of the following Chemical Formula 9 can be used.

Chemical Formula

[0126] 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 it is 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.

[0127] 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 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.

[0128] 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 phenylenyl group, a chrysenyl group, or a fluorenyl group, etc., and 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 pyrimidyl 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.

[0129] 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.

[0130] In one exemplary embodiment, 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 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. In some cases, at least one of the carbon atoms constituting the alkylidene group may be substituted with an oxygen atom.

[0131] 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).

[0132] 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.

[0133] The thiol compound may be a compound in which one of the hydrogen atoms of a hydrocarbon compound such as an 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.

[0134] The alkane, alkene or alkynyl halogen 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, an alkoxy group having 1 to 4 carbon atoms and / or a silyl group (for example, the substituent represented by -Si(R3)3 in Chemical Formula 9 above).

[0135] 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 a 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.

[0136] There are no particular restrictions on the specific types of the thiol compounds as described above. For example, it may be 1-dodecane thiol or (3-mercaptopropyl)triethoxy silane, etc.

[0137] When the 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 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 0.001 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 above-mentioned lower limits or above any one of the above-mentioned lower limits and below any one of the above-mentioned upper 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.

[0138] When the thiol compound and the catalyst are simultaneously included in the polyurethane composition, their proportions can be controlled.

[0139] 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 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.

[0140] In the above, as the carboxylic acid compound, for example, a monofunctional compound having a hydrocarbon group may be used. The fact that the carboxylic acid compound is a monofunctional compound means that the compound contains one carboxyl group (-COOH).

[0141] 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.

[0142] 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.

[0143] The carboxylic acid compound may be a compound in which one of the hydrogen atoms in a hydrocarbon compound such as an alkane, an alkene or an 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.

[0144] 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 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.

[0145] As the carboxylic acid compound, a compound with 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.

[0146] There are no particular restrictions on the specific type of the carboxylic acid compound. For example, it may be acetic acid, stearic acid, 2-ethylhexanoic acid, isononanoic acid, oleic acid, or the like.

[0147] 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 or 1 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, 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.

[0148] In the case where the carboxylic acid compound and the catalyst are simultaneously contained in the polyurethane composition, their ratios can be controlled. 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 or 2, and the upper limit thereof may be about 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 above any one of the lower limits described above and 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.

[0149] 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 section after the start of curing, secure an appropriate curing rate and curability after the lapse of the viscosity maintenance section, and simultaneously enable adjustment of the hardness increase rate, the carboxylic acid compound and the thiol compound can be applied simultaneously.

[0150] When the thiol compound and the carboxylic acid compound are simultaneously contained 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 above any one of the lower limits described above and 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.

[0151] 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 (e.g., thixotropic agents, diluents, etc.) for adjusting viscosity, such as increasing or reducing viscosity or adjusting viscosity by shear force, dispersants, surface treatment agents, flame retardants, flame retardant aids, and / or coupling agents, etc., but are not limited thereto.

[0152] As described above, the resin composition may be a one-component composition or a two-component composition. In the case of a two-component composition, each of the above-described components of the resin composition can be contained separately in a physically separated main agent part and curing agent part.

[0153] In one exemplary embodiment, the present application relates to a composition (two-component composition) in which the resin composition consists of a two-component composition. Such a two-component composition may contain at least a main agent part and a curing agent part, 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 can be initiated. When the resin composition is a polyurethane composition, polyurethane can be formed as a result of the curing reaction.

[0154] When constructing a two-component composition, the main agent part may contain at least the curable component, catalyst, and curing rate regulator among the above-described components. Also, the curing agent part may contain at least the curing agent (polyisocyanate). In the above cases, the main agent part does not contain the curing agent (polyisocyanate), and the curing agent part does not necessarily contain the curable component, catalyst, and curing regulator.

[0155] The filler component may be contained in either one of the main agent and curing agent parts, or may be contained in both the main agent and curing agent parts. When the filler component is entirely contained in the main agent and curing agent parts, the same amount of filler component may be contained in the main agent and curing agent parts. For example, in the above case, the upper limit of the proportion of the filler component in the main agent 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.

[0156] The proportion of the filler component in the main agent part can also be defined as the proportion with respect to 100 parts by weight of the total weight of the curable component of the main agent part or the reactive compound present in the curable component. 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 or 850 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 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.

[0157] In the above-described 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 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.

[0158] 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 or 850 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 proportion 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. Other components such as catalysts, plasticizers, and flame retardants can be included in the main agent and / or hardener part as necessary.

[0159] 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.

[0160] In one example, the two-component composition can be formulated so that when the main agent part and the curing agent part have the volume ratio, the aforementioned equivalent ratio (OH / NCO) can be ensured. Such a two-component composition or its cured product can also exhibit the adhesion 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.

[0161] The resin composition (one-component or two-component composition) can exhibit an appropriate curing rate after the start of curing. In the above, the start of curing occurs when the curable component and the curing agent contained in the resin composition come into contact under conditions where curing can be initiated. Therefore, in the case of a one-component composition, curing starts when the composition is placed under curing start conditions, and in the case of a two-component composition, the curing can start when the main agent and the curing agent parts are mixed under curing start conditions.

[0162] For example, when the resin composition is a curable composition, the curable composition can exhibit a curing rate such that V1 according to the following formula 1 is within a predetermined range. [Formula 1] V1 = V initial / t In formula 1, V initialis the initial viscosity (unit: cps) at the start of curing of the curable composition, and t is the time (unit: minutes) required for the viscosity of the curable composition to become twice the initial viscosity from the start of curing.

[0163] As described above, the curing occurs when the components participating in the curing reaction come into contact under conditions where curing is possible. For example, when the curable composition is a main agent part containing the curable component, a curing rate regulator, a urethane reaction catalyst, and a filler component, the start of curing may be the time when the main agent part (curable composition) and the curing agent component (for example, the curing agent component containing the polyisocyanate or the curing agent part) are mixed under conditions where curing is possible. The mixing for confirming V1 in the following formula 1 can be performed so that the main agent part and the curing agent component satisfy the volume ratio (P / N) and / or the equivalent ratio (OH / NCO) described above.

[0164] Therefore, in such a case, the initial viscosity may be the initial viscosity of the mixture of the main agent part and the curing agent component. The method for confirming V1 in the formula 1 is arranged in the examples. The lower limit of V1 in the formula 1 may be about 2,000 cps / min, 2,500 cps / min, 3,000 cps / min, 3,500 cps / min, 4,000 cps / min, 4,500 cps / min, 5,000 cps / min, 5,500 cps / min, 6,000 cps / min or 6,500 cps / min, and the upper limit thereof may be about 20,000 cps / min, 18,000 cps / min, 16,000 cps / min, 14,000 cps / min, 12,000 cps / min, 10,000 cps / min, 9,500 cps / min, 9,000 cps / min, 8,500 cps / min, 8,000 cps / min, 7,500 cps / min, 7,000 cps / min, 6,500 cps / min, 6,000 cps / min, 5,500 cps / min, 5,000 cps / min, 4,500 cps / min, 4,000 cps / min, 3,500 cps / min, 3,000 cps / min or 2,500 cps / min. The V1 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.

[0165] In the formula 1, the upper limit of V initial may be about 400,000 cps, 350,000 cps, 300,000 cps, 250,000 cps, 200,000 cps or 150,000 cps, and the lower limit thereof may be about 10,000 cps, 50,000 cps, 100,000 cps, 150,000 cps or 200,000 cps. The V initial 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.

[0166] The curable composition can exhibit a predetermined Shore OO hardness detection time after the start of curing. In the above, the Shore OO hardness detection time means the time taken for the Shore OO hardness to be first detected (detection) in the process of periodically measuring the hardness of the curable composition after the start of curing. That is, when the curable composition is placed under the curing start conditions, the hardness increases as curing progresses. Therefore, if the Shore OO hardness detection time is short, it means that the curing rate is fast. In the above, the meaning of the start point of curing and the curable composition for which the hardness is measured is as described in Formula 1 above.

[0167] Therefore, for example, when the curable composition is the main agent part containing the curable component, the curing rate regulator, the urethane reaction catalyst, and the filler component, the start point of curing may be the time when the main agent part (curable composition) and the curing agent component (for example, the curing agent component containing the polyisocyanate or the curing agent part) are mixed under curable conditions, and the mixing can be carried out so that the main agent part and the curing agent component satisfy the above-described volume ratio (P / N) and / or equivalent ratio (OH / NCO). In such a case, the hardness can be measured for the mixture of the main agent part and the curing agent component.

[0168] The lower limit of the Shore OO hardness detection time may be about 60 minutes, 80 minutes, 100 minutes, 150 minutes, 200 minutes, 250 minutes, 300 minutes, 350 minutes, 400 minutes, 450 minutes, 500 minutes, 550 minutes, 600 minutes, 650 minutes, 700 minutes, or 750 minutes, and the upper limit may be about 30 hours, 28 hours, 26 hours, 24 hours, 22 hours, 20 hours, 18 hours, 16 hours, 14 hours, 12 hours, 10 hours, 9 hours, 8 hours, 7 hours, 6 hours, 5 hours, or 4 hours. The detection time may be within a range that is equal to or greater than any one of the above-described lower limits, equal to or less 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.

[0169] This application also relates to a thermal interface material (TIM). The thermal interface material may be a cured product of the resin composition.

[0170] Therefore, the thermal interface material can also exhibit the adhesion 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) as described above.

[0171] Therefore, the thermal interface material may contain components included in the resin composition or components derived from such components. For example, when the resin composition is a polyurethane composition, the thermal interface material may contain the polyurethane. Polyurethane can be formed by the reaction of the reactive compound described above and a curing agent (polyisocyanate).

[0172] Therefore, the polyurethane may contain units derived from the reactive compound. For example, when the reactive compound contains the polyester backbone (e.g., polycaprolactone backbone) or polyether backbone (e.g., polyalkylene backbone) described above, the polyurethane may contain the polyester unit (e.g., polycaprolactone unit) or polyether unit (e.g., polyalkylene unit). For example, the polyurethane may contain the units of Chemical Formulas 2, 3, 5, and / or 6 described above. In addition, the polyurethane may contain a hydrocarbon group derived from the oil-modified compound described above, that is, a linear or branched hydrocarbon group having 3 or more carbon atoms.

[0173] As described above, the lower limit of the number of carbon atoms of the linear or branched hydrocarbon group may be about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, and the upper limit 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 less than or equal to any one of the upper limits described above, greater than or equal to any one of the lower 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.

[0174] 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.

[0175] 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 polyurethane skeleton 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 equal to or greater than any one of the lower limits of the number of carbon atoms of the linear or branched hydrocarbon group described above, equal to or less than any one of the upper limits of the number of carbon atoms of the linear or branched hydrocarbon group described above, 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.

[0176] 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 a substituent. As described above, the hydrocarbon group may be included in the structures of Chemical Formulas 1 to 6 described above.

[0177] In addition, since the polyurethane may contain units derived from the curable component described above, it may contain units of the first reactive compound and units of the second reactive compound. As the units of the second reactive compound, it may contain units of the third reactive compound and units of the fourth reactive compound. Specific descriptions of the reactive compounds and the ratios between them can be applied identically to the content described in the resin composition.

[0178] In addition, since the polyurethane may contain units derived from the above-described curing agent, it may contain the above-described polyisocyanate units. For example, it may contain trifunctional or higher polyisocyanate units and bifunctional polyisocyanate units. Specific descriptions of the polyisocyanate and the ratios between them can be applied identically to the content described in the resin composition.

[0179] The polyurethane contained in the thermal interface material may contain at least one hydroxy group. That is, the polyurethane can be synthesized by the reaction of the hydroxy group of the reactive compound and the isocyanate group of the polyisocyanate as the curing agent to form a urethane bond. By further adjusting the hydroxy group equivalent of the reactive compound in this process, at least one hydroxy group can be left in the final polyurethane. For example, the polyurethane may contain hydroxy groups in an amount of 0.1 mol / g or more, 0.1 mol / g to 10 mol / g, 0.1 mol / g to 9 mol / g, 0.1 mol / g to 8 mol / g, 0.1 mol / g to 7 mol / g, 0.1 mol / g to 6 mol / g, 0.1 mol / g to 5 mol / g, 0.1 mol / g to 4 mol / g, 0.1 mol / g to 3 mol / g, 0.1 mol / g to 2 mol / g, 0.1 mol / g to 1 mol / g, or about 0.1 mol / g to 0.5 mol / g. By leaving hydroxy groups in the polyurethane at the above ratios, a thermal interface material having the desired properties can be formed more effectively. There are no special restrictions on the method of leaving hydroxy groups in the polyurethane as described above, and the equivalent ratio of OH / NCO can be adjusted during the reaction process to form the above-described polyurethane.

[0180] The thermal interface material may contain, together with the polyurethane, components of the resin composition described above, such as a curing rate regulator, a plasticizer, a catalyst, and / or a filler component. Specific descriptions of the components and the weight ratios thereof can be applied identically to the content in the resin composition. This application also relates to a product containing the resin composition or its cured product (thermal interface material or heat transfer material). The resin composition or its cured product of this application can be usefully applied as a heat dissipation material. Therefore, the product may include heat-generating components. 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 such as battery cells, battery modules, or battery packs.

[0181] The product of this application may include, for example, the heat-generating component and the resin composition (or the two-component composition) and its cured product that are present adjacent to the heat-generating component. The specific method for constructing the product of this application is not particularly limited. When the resin composition, two-component composition, or its cured product of this application is applied as a heat dissipation material, the product can be constructed in various known ways.

Advantages of the Invention

[0182] This application provides a curable composition, a thermal interface material (TIM: Thermal Interface Material), and its uses. In this application, the curable composition or thermal interface material, etc., can exhibit high thermal conductivity while showing low adhesion to a predetermined adherend. Also, in this application, the low adhesion can be achieved without using an adhesion-adjusting component such as a plasticizer or by minimizing its usage ratio. In this application, the curable composition can also be made to have a precisely controlled curing rate while having excellent curability. In this application, a product containing the curable composition, its cured product, or a thermal interface material can also be provided.

Brief Description of the Drawings

[0183]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Embodiments for Carrying Out the Invention

[0184] Hereinafter, the present application will be specifically described based on examples, but the scope of the present application is not limited by the following examples. The cured body mentioned below was formed by mixing the main component part and the curing agent part of the resin composition of the example produced in a two-component type so as to satisfy the OH / NCO equivalent ratio described in each example, and then maintaining it at room temperature (about 25°C) for about 24 hours.

[0185] In this example, the physical properties were evaluated by the following method. 1. Thermal conductivity The thermal conductivity of the resin composition (curable composition) or its cured body was measured by the hot disk method according to the ISO22007-2 standard. Specifically, a mixture obtained by mixing the main component part and the curing agent part of the example or comparative example at a volume ratio of 1:1 was placed in a mold having a thickness of about 7 mm, and the thermal conductivity was measured in the film thickness direction (through-plane) using a hot disk apparatus. As defined in the said standard (ISO22007-2), the hot disk apparatus is an apparatus capable of measuring the thermal conductivity by measuring the temperature change (change in electrical resistance) when a sensor in which a nickel wire has a double spiral structure is heated, and the thermal conductivity was measured according to such a standard.

[0186] 2. Measurement of Adhesion to Polyester The adhesive strength to the polyester was evaluated with respect to a test piece produced by adhering a PET (polyethylene terephthalate) film and 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 entirely coated on the surface of the aluminum plate, and the test piece was produced by maintaining it at room temperature (about 25°C) for about 24 hours with the PET film adhered on the resin composition. 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 adhesive strength 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 agent part and the curing agent part with a volume ratio of 1:1) to the aluminum plate so that the thickness after curing would be 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.

[0187] 3. Measurement of Adhesive Strength to Aluminum An uncured resin composition (a mixture of the main agent part and the curing agent part with 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 would be about 2 cm. 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 adhesive strength to aluminum was obtained by dividing the maximum value of the force measured in the process by the area of the test piece.

[0188] 4. Measurement of Hardness The hardness of the cured 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 (cured body), and the hardness was evaluated by confirming the measured value stabilized after 15 seconds.

[0189] 5. Measurement of Viscosity The viscosity was measured at room temperature (about 25°C) using a Brookfield HB DB3T type instrument under shear rate conditions from 0.01 s -1 to 10.0 s -1 . Unless otherwise specified, the viscosity referred to in this specification is the viscosity at a shear rate of 2.4 s -1 .

[0190] 6. Measurement of Curing Rate (Hardness Confirmation Time) 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 as described above. 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 hardness was confirmed every 30 minutes, and the time when the Shore OO hardness was first confirmed was confirmed to evaluate the curing rate.

[0191] 7. Measurement of Curing Rate (Viscosity Increase Time) The curing rate of the resin composition was also evaluated through the change in viscosity over time. Specifically, V1 in the following formula 1 was confirmed to evaluate the curing rate. [Formula 1] V1 = V initial / t In formula 1, V initial is the initial viscosity (unit: cps) of the mixture obtained by mixing the curable composition with a curing agent component having polyisocyanate, and t is the time (unit: minutes) required for the viscosity of the mixture to become twice the initial viscosity.

[0192] Specifically, for the V initial a mixture obtained by mixing the main agent part and the curing agent part produced in the example or comparative example at a volume ratio of 1:1 was loaded into a viscosity measuring instrument (Brookfield HB DB3T type instrument), and the viscosity was measured after maintaining a shear rate of 2.4 s -1 for about 60 seconds while maintaining the shear rate, and stabilizing the viscosity. The viscosity was measured over time while loaded into a Brookfield HB DB3T type viscometer and maintaining a shear rate condition of 2.4 s -1 .

[0193] 8. Measurement of Bending Radius The bending radius of the cured body was evaluated using a cured body 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 body is attached to a cylinder with various radii and bent along the longitudinal direction, and no crack occurs in the cured body.

[0194] 9. 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 Marvern 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 obtained. The distribution is obtained by converting to the diameter of a sphere having the same volume as the filler dispersed through the analysis, and thereby the D50 value, which is the median of the distribution, can be obtained to evaluate the particle size.

[0195] 10. Evaluation of Module Workability A resin composition (a mixture of a main agent and a 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 horizontally and vertically, and with a thickness of about 2 mm, and maintained at room temperature (about 25 °C) and normal humidity (about 40% relative humidity) for about 24 hours to cure. Next, while peeling the cured product from the aluminum plate, the module workability was evaluated according to the following criteria. <Evaluation Criteria> ○: When the cured product of the resin composition peels off in a sheet form without leaving residues on the aluminum plate ×: When it is impossible to peel the cured product of the resin composition from the aluminum plate, or residues remain even after peeling

[0196] 11. Evaluation of Purge Waiting Time The purge waiting time was evaluated by measuring the load value. The load value (unit: kgf) was evaluated using an apparatus as shown in Fig. 1. The apparatus of Fig. 1 is an apparatus 1 in which two cartridges 2, 2a, 2b and one static mixer 5 are connected. In the apparatus 1, as the cartridges 2, 2a, 2b, 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 cartridges (Sulzer, AB050 - 01 - 10 - 01) were used. As the static mixer 5, a stepped type static mixer (Sulzer, MBH - 06 - 16T) with a discharge part 7 having a circular diameter of 2 mm and 16 elements was used. As the pressurizing means 3, 3a, 3b (means for extruding the composition loaded in the cartridge) of the apparatus, TA (Texture analyzer) was used.

[0197] For the measurement of the load value, the main agent part was loaded into one of the two cartridges 2a and 2b, and the curing agent part was loaded into the other cartridge. Next, the pressurizing means 3, 3a, and 3b were used to pressurize at a constant speed of 1 mm / sec, and the main agent and the curing agent parts were injected into the static mixer 5, mixed by the mixer 5, and discharged from the discharge part 7. During the above process, the force applied to the pressurizing means from the start of pressurization by the pressurizing means until the discharge was measured. The maximum value of the force applied to the pressurizing means during the above process was taken as the load value. After measuring the load value, the pressurization was interrupted, and the apparatus 1 was maintained at room temperature (about 25°C). In such a case, the mixture of the main agent part and the curing agent part was maintained in the mixer 5. After waiting for a certain period of time, the pressurization was started again by the pressurizing means, and the load value was measured in the same manner as above. The waiting time when the load value reached 60 kgf during this process was taken as the purging waiting time.

[0198] 12. Measurement of weight average molecular weight The weight average molecular weight (Mw) was measured using GPC (Gel permeation chromatography). Specifically, for the measurement of the weight average molecular weight (Mw), the sample to be analyzed was placed in 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.

[0199] <GPC measurement conditions> Equipment: 1200 series of Agilent technologies Column: TL Mix.A&B of Agilent technologies was used Solvent: THF (tetrahydrofuran) Column temperature: 35°C Sample concentration: 1 mg / mL, 200 μL injection Standard sample: Polystyrene (MP: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485) was used

[0200] 13. GC-MS (Gas Chromatography-Mass Spectrometry) analysis As the measuring instrument for GC-MS analysis, an Agilent instrument was used (GC (Gas Chromatography) instrument: 7890 model, MS (Mass Spectrometry) Detector: 5977B model). The sample (cured product of the resin composition) was dissolved in a solvent (chloroform) at a concentration of 100 mg / mL, the supernatant was extracted, filtered through a 0.2 μm syringe filter, and then loaded onto the GS-MS analysis instrument. Analysis was carried out under the following conditions, and quantitative analysis was carried out through the intensity of the peaks of the target substances to be detected (1-dodecanethiol and 2-ethylhexanoic acid).

[0201] <GC measurement conditions> Column: HP-5MS from Agilent technologies Gas flow rate: Column (He): 1 mL / min Ionization mode: EI Injection temperature: 300°C Injection volume: 0.5 μL

[0202] Production Example 1. The oil-modified compound (reactive compound) of the following Chemical Formula A was produced in the following manner.

Chemical formula

[0203] As a result of GPC analysis performed on the target product, the weight average molecular weight was at a level of about 710 g / mol. Figure 2 is a diagram showing the results of GPC analysis performed on the target product.

[0204] Production Example 2. The oil-modified compound (reactive compound) of the following Chemical Formula B was produced in the following manner.

Chemical formula

[0205] In Chemical Formula B, p and q are each greater than 0, and their sum (p + q) is about 4.8. Polycaprolactone polyol (Perstorp's Capa 3031) and isononanoic acid, a saturated fatty acid, were mixed at a weight ratio of 1:1.06 (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 (the compound of Chemical Formula B).

[0206] As a result of GPC analysis performed on the target product, the weight average molecular weight was at the level of about 814 g / mol. Figure 3 is a diagram showing the results of GPC analysis performed on the target product.

[0207] Example 1. Manufacture of the main agent part The oil-modified compound, non-oil-modified compound (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component and plasticizer (diisononyl adipate) of Production Examples 1 and 2 were mixed at a weight ratio of 4.59:5.1:0.51:0.066:0.2:0.066:88.8:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer) to manufacture the main agent part. 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, and a third alumina filler with an average particle size of about 1 μm were mixed and manufactured. The volume ratio at the time of the mixing was set to about 6:2:2 (first alumina filler: second alumina filler: third alumina filler).

[0208] Manufacture of the curing agent part Polyisocyanate (Tolonate HDT-LV2, manufactured by Vencorex) was used as the curing agent. The polyisocyanate, filler component, and plasticizer (diisononyl adipate) were mixed at a weight ratio of 5.08:4.78:90.1 (polyisocyanate: filler: plasticizer) to produce the main agent part. 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, and a third alumina filler with an average particle size of about 1 μm were mixed and produced. The volume ratio during the mixing was about 6:2:2 (first alumina filler: second alumina filler: third alumina filler). The curing agent part was manufactured such that when the curing agent part was blended with the main agent part at a volume ratio of 1:1, the equivalent ratio (OH / NCO) of the hydroxy group (OH) present in the main agent part and the isocyanate group (NCO) present in the curing agent part was about 100.

[0209] Production of Resin Composition and Cured Body The main agent and the curing agent part were each prepared to produce a resin composition (curable composition). After mixing the main agent and the curing agent part at a volume ratio of about 1:1, they were maintained at room temperature (about 25°C) to form a cured body.

[0210] Example 2. The main agent part was produced in the same manner as in Example 1, except that the blending weight ratios of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component, and plasticizer (diisononyl adipate) in Production Examples 1 and 2 were changed to 4.59:5.1:0.51:0.048:0.096:0.096:88.9:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer). The curing agent part, resin composition, and cured body were produced in the same manner as in Example 1.

[0211] Example 3 The main component parts were produced in the same manner as in Example 1, except that the compounding weight ratios of the oil-modified compounds, non-oil-modified compounds (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component, and plasticizer (diisononyl adipate) of Production Examples 1 and 2 were changed to 4.59:5.1:0.51:0.06:0.11:0.11:88.8:0.71 (Production Example 1:Production Example 2:F-2010:DBTDL:thiol:2-EHA:filler:plasticizer). The curing agent parts, resin compositions, and cured bodies were produced in the same manner as in Example 1.

[0212] Example 4 The main component parts were produced by blending the oil-modified compounds, non-oil-modified compounds (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component, and plasticizer (diisononyl adipate) of Production Examples 1 and 2 at a weight ratio of 4.59:5.1:0.51:0.03:0.055:0.055:89:0.71 (Production Example 1:Production Example 2:F-2010:DBTDL:thiol:2-EHA:filler:plasticizer). The same filler component as in Example 1 was used. The curing agent parts, resin compositions, and cured bodies were produced in the same manner as in Example 1.

[0213] Example 5 The oil-modified compounds of Production Examples 1 and 2, non-oil-modified compound (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component, and plasticizer (diisononyl adipate) were blended at a weight ratio of 4.59:5.1:0.51:0.018:0.033:0.033:89:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer) to produce the main agent parts. The same filler component as in Example 1 was used. The curing agent parts, resin composition, and cured body were produced in the same manner as in Example 1.

[0214] Example 6. The oil-modified compounds of Production Examples 1 and 2, non-oil-modified compound (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component, and plasticizer (diisononyl adipate) were blended at a weight ratio of 4.59:5.11:0.51:0.012:0.022:0.022:89:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer) to produce the main agent parts. The same filler component as in Example 1 was used. The curing agent parts, resin composition, and cured body were produced in the same manner as in Example 1.

[0215] Example 7. The oil-modified compounds of Production Examples 1 and 2, non-oil-modified compound (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component and plasticizer (diisononyl adipate) were blended at a weight ratio of 4.6:5.11:0.51:0.0066:0.011:0.011:89:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer) to produce the main agent parts. The same filler component as in Example 1 was used. The curing agent parts, resin composition and cured body were produced in the same manner as in Example 1.

[0216] Comparative Example 1. The main agent parts, curing agent parts, resin composition and cured body were produced in the same manner as in Example 1, except that the thiol compound and carboxylic acid compound were not used during the production of the main agent parts.

[0217] Comparative Example 2. The main agent parts were produced in the same manner as in Example 1, except that the blending weight ratio of the oil-modified compounds of Production Examples 1 and 2, non-oil-modified compound (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component and plasticizer (diisononyl adipate) was changed to 4.59:5.10:0.51:0.066:0.13:88.9:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent parts, resin composition and cured body were produced in the same manner as in Example 1.

[0218] Comparative Example 3. The main agent parts were produced in the same manner as in Example 1, except that the compounding weight ratios of the oil-modified compounds, non-oil-modified compound (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), filler component, and plasticizer (diisononyl adipate) in Production Examples 1 and 2 were changed to 4.59:5.1:0.51:0.066:0.13:88.9:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: thiol: filler: plasticizer). The hardener parts, resin compositions, and cured bodies were produced in the same manner as in Example 1.

[0219] Comparative Example 4. The main agent parts were produced in the same manner as in Example 1, except that the compounding weight ratios of the oil-modified compounds, non-oil-modified compound (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), filler component, and plasticizer (diisononyl adipate) in Production Examples 1 and 2 were changed to 4.59:5.1:0.51:0.066:0.153:88.9:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: thiol: filler: plasticizer). The hardener parts, resin compositions, and cured bodies were produced in the same manner as in Example 1.

[0220] Comparative Example 5. The main agent parts were produced in the same manner as in Example 1, except that the compounding weight ratios of the oil-modified compounds, non-oil-modified compound (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), filler component, and plasticizer (diisononyl adipate) in Production Examples 1 and 2 were changed to 4.59:5.1:0.51:0.066:0.2:88.8:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: thiol: filler: plasticizer). The hardener parts, resin compositions, and cured bodies were produced in the same manner as in Example 1.

[0221] Comparative Example 6. The main agent parts were produced in the same manner as in Example 1, except that the compounding weight ratios of the oil-modified compounds, non-oil-modified compounds (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), filler component, and plasticizer (diisononyl adipate) in Production Examples 1 and 2 were changed to 4.6:5.11:0.51:0.048:89:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: filler: plasticizer). The curing agent parts, resin compositions, and cured bodies were produced in the same manner as in Example 1.

[0222] Comparative Example 7. The main agent parts were produced in the same manner as in Example 1, except that the compounding weight ratios of the oil-modified compounds, non-oil-modified compounds (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), filler component, and plasticizer (diisononyl adipate) in Production Examples 1 and 2 were changed to 4.59:5.1:0.51:0.048:0.096:89:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: thiol: filler: plasticizer). The curing agent parts, resin compositions, and cured bodies were produced in the same manner as in Example 1.

[0223] Comparative Example 8. The main agent parts were produced in the same manner as in Example 1, except that the compounding weight ratios of the oil-modified compounds, non-oil-modified compounds (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component, and plasticizer (diisononyl adipate) in Production Examples 1 and 2 were changed to 4.59:5.1:0.51:0.048:0.096:89:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent parts, resin compositions, and cured bodies were produced in the same manner as in Example 1.

[0224] Comparative Example 9. The main component parts were produced in the same manner as in Example 1, except that the blending weight ratios of the oil-modified compounds, non-oil-modified compounds (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), thiol compound (1-dodecanethiol), filler component, and plasticizer (diisononyl adipate) in Production Examples 1 and 2 were changed to 4.59:5.1:0.51:0.06:0.11:88.9:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: thiol: filler: plasticizer). The curing agent parts, resin compositions, and cured bodies were produced in the same manner as in Example 1.

[0225] Comparative Example 10. The main component parts were produced in the same manner as in Example 1, except that the blending weight ratios of the oil-modified compounds, non-oil-modified compounds (Kuraray, F-2010), urethane reaction catalyst (DBTDL, Dibutyltin dilaurate), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component, and plasticizer (diisononyl adipate) in Production Examples 1 and 2 were changed to 4.59:5.10:0.51:0.060:0.11:88.9:0.71 (Production Example 1: Production Example 2: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent parts, resin compositions, and cured bodies were produced in the same manner as in Example 1.

[0226] The physical property evaluation results organized for each of the above Examples and Comparative Examples are as shown in Tables 1 to 4 below. In Tables 1 and 2 below, the hardness (Shore OO and Shore A hardness) is the hardness measured after maintaining a 1:1 volume ratio mixture of the main component part and the curing agent part at room temperature (about 25°C) for 24 hours. In Tables 1 to 4 below, the curing rate (hardness) is the time (unit: hour) when the Shore OO hardness is first confirmed when the main component part and the curing agent part of the Example or Comparative Example are mixed at a 1:1 volume ratio and the hardness is confirmed every 30 minutes while maintaining at room temperature (about 25°C) (related to the above measurement 6. Measurement of curing rate (hardness confirmation time)). In Tables 1 to 4 below, the curing rate (viscosity) is t (unit: minutes) in the formula 1 by the method for measuring the curing rate (viscosity increase time), and V initial and V1 are respectively V in the formula 1 initial and V1.

[0227]

Table 1

[0228]

Table 2

[0229]

Table 3

[0230]

Table 4

[0231] Test Example 1. To confirm the curing delay effect by the action of the thiol compound and the carboxylic acid compound, evaluations were carried out on the resin compositions of Example 1, Comparative Examples 1, 2 and 5. The main agent part and the curing agent part of the resin composition of each of the above Examples or Comparative Examples were mixed at a volume ratio of 1:1, and the changes in viscosity and hardness over time were evaluated, and the results are shown in FIGS. 4 and 5. Referring to the drawings, in the case of Example 1 containing both the thiol compound and the carboxylic acid compound, a viscosity maintenance section where the viscosity after mixing is maintained was confirmed, and it can be confirmed that the viscosity rapidly increases after the viscosity maintenance section, and the curability is stably ensured after the curing delay. Also, from the viewpoint of hardness, it can be confirmed that there is a section where the proper time hardness is not measured. It can be seen that immediately after mixing the main agent and the curing agent parts of Comparative Example 1 that does not contain the thiol compound and the carboxylic acid compound, the viscosity rapidly increases, and the hardness also begins to increase at an early point immediately after mixing.

[0232] In the case of Comparative Example 2 containing only the carboxylic acid compound, although the tendency of the viscosity to increase was confirmed slowly compared to Comparative Example 1, there was no viscosity maintenance section where the viscosity was maintained constant in the initial stage of mixing, the hardness was confirmed to be excessively slow, and it was found that the viscosity increase did not go well even over time and the curability was insufficient. In the case of Comparative Example 5 containing only the thiol compound, a viscosity maintenance section was observed, but it was found that the viscosity maintenance section was relatively short and the viscosity increase rate was excessively fast after the passage of the viscosity maintenance section. Also, in the case of Comparative Example 5, the hardness also increased excessively rapidly, and it could be predicted that it would not be easy to secure the working time in a large-area coating process or the like.

[0233] Test Example 2. Table 5 below summarizes the contents of the thiol compound and the carboxylic acid compound in the main agent parts and the cured bodies of Examples 2 to 7. In Table 5 below, the blending amount is the amount of the thiol compound and the carboxylic acid compound added during production (unit: wt%), and the detected amount is the amount detected by GC-MS (Gas Chromatography-Mass Spectrometry) analysis (unit: wt%).

[0234] From the results in Table 5, it can be seen that the thiol compound and the carboxylic acid compound added to the main agent part also remain in the cured body after the curing reaction. In Examples 5 to 8, there were cases where the thiol compound and / or the carboxylic acid compound were not detected, but this was the result of a small addition amount. Considering the results of Examples 2 to 4, it can be inferred that the carboxylic acid compound and the thiol compound also exist in the cured bodies of Examples 5 to 8.

[0235]

Table 5

Claims

1. A curable component containing a reactive compound having a hydroxy group; One or more curing rate regulators selected from the group consisting of a thiol compound and a carboxylic acid compound; A urethane reaction catalyst and A filler component, V according to the following formula 1 １ A curable composition having curability within the range of 2,000 to 20,000 cps / min: [Formula 1] V １ = V ｉｎｉｔｉａｌ / t In Formula 1, V ｉｎｉｔｉａｌ is the initial viscosity (unit: cps) of a mixture obtained by mixing the curable composition with a curing agent component having a polyisocyanate, and t is the time (unit: minutes) required for the viscosity of the mixture to become twice the initial viscosity.

2. A curable component containing a reactive compound having a hydroxy group; One or more curing rate regulators selected from the group consisting of a thiol compound and a carboxylic acid compound; A urethane reaction catalyst and A filler component, A curable composition having a curability with a Shore OO hardness detection time of 60 minutes or more.

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

4. The curable composition according to claim 3, 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.

5. The curable composition according to claim 1 or 2, wherein the reactive compound contains a branched hydrocarbon chain having 5 or more carbon atoms at the terminal.

6. The curable composition according to claim 4, wherein the first and third reactive compounds each contain a branched hydrocarbon chain having 5 or more carbon atoms at the terminal.

7. The curable composition according to claim 4, wherein the fourth reactive compound contains a polycaprolactone polyol unit or an alkanediol unit; a polyol unit and a dicarboxylic acid unit.

8. The curable composition according to claim 1 or 2, wherein the thiol compound is a monofunctional compound having a hydrocarbon group.

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

10. The curable composition according to claim 1 or 2, wherein the carboxylic acid compound is a monofunctional compound having a hydrocarbon group.

11. The curable composition according to claim 10, wherein the monofunctional compound has a molecular weight in the range of 50 to 400 g / mol.

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

13. The curable composition according to claim 1 or 2, wherein the curing rate regulator is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the curable component.

14. The hardening rate regulator is a curable composition according to claim 1 or 2, which contains a thiol compound and a carboxylic acid compound.

15. The urethane reaction catalyst is a tin catalyst, and the curable composition is as described in claim 1 or 2.

16. The curable composition according to claim 14, wherein the weight ratio of the thiol compound to the carboxylic acid compound is in the range of 1 to 5.

17. The curable composition according to claim 14, wherein the weight ratio of the thiol compound to the urethane reaction catalyst is in the range of 1 to 5.

18. The curable composition according to claim 1 or 2, which forms a cured body having a thermal conductivity of 2.0 W / mk or more.

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

20. The curable composition according to claim 1 or 2, which forms a cured body having an adhesive force to polyester of 100 gf / cm or less.

21. The curable composition according to claim 1 or 2, which forms a cured body having a Shore OO hardness of 95 or less.

22. The curable composition according to claim 1 or 2, which further contains a plasticizer.

23. The curable composition according to claim 1 or 2, which contains 500 parts by weight or more of a filler component based on 100 parts by weight of the curable component.

24. A two-component composition containing a main agent part and a curing agent part, The two-component composition, wherein the main agent part is a curable composition according to any one of claims 1 to 23.

25. Containing a heating element and a thermally conductive material existing adjacent to the heating element, A product, wherein the thermally conductive material contains a cured body of the curable composition according to claim 1 or the two-component composition according to claim 24.

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