Curable composition

Abstract

Curable compositions, thermal interface materials (TIMs), and uses thereof are provided. In the present application, a curable composition, a thermal interface material or the like may exhibit a low adhesive force to a given adherend while exhibiting a high thermal conductivity. Further, in the present application, a low adhesive force can be achieved without using an adhesive force adjusting component such as a plasticizer or in a state in which the use ratio thereof is minimized. In the present application, the curable composition may also exhibit a precisely controlled curing rate and at the same time have excellent curability. The present application may also provide a product comprising the curable composition or a cured body thereof or a thermal interface material.

Description

Technical Field

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0116478, dated September 15, 2022, the disclosure of which is incorporated herein by reference in its entirety.

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

[0003] As the number of electrical or electronic devices (e.g., batteries) that require thermal management increases, the importance of heat dissipation materials such as thermal interface materials (TIM) increases. Various types of heat dissipation materials are known. As one of the conventional heat dissipation materials, a material in which a resin binder is filled with a filler having heat dissipation properties is known (e.g., Patent Document 1).

[0004] In such heat dissipation materials, silicone resin, polyolefin resin, acrylic resin, epoxy resin, or the like is generally used as a resin binder.

[0005] The heat dissipation material is basically required to have excellent thermal conductivity, and may also have additional functions depending on the application. For example, the heat dissipation material may need to exhibit low adhesion to a specific adherend and high thermal conductivity depending on the application.

[0006] For example, when a component in contact with the heat dissipation material in a product needs to be replaced or the position of the heat dissipation material needs to be changed during a process, the heat dissipation material needs to exhibit low adhesion.

[0007] Among known heat dissipation materials, materials showing low adhesion include materials using silicone resin as a resin binder. However, silicone resin is relatively expensive. In addition, silicone resin contains components that cause contact failures when applied to electronic / electrical products, so that the use is limited.

[0008] Even though the polyurethane material applied in Patent Document 1 can form a heat dissipation material having high thermal conductivity and has various other advantages, it is a material that exhibits high adhesive force to most adherends.

[0009] Methods for reducing the adhesive force of materials showing high adhesive force include a method of blending a component called a so-called plasticizer. However, a plasticizer formulated in large amounts for the purpose of controlling adhesive force has problems such as destroying the inherent advantages of the material itself or being dissolved during use.

[0010] At the same time, for the heat dissipation material with curability, it is necessary to control the curing speed of the relevant heat dissipation material.

[0011] That is, when a heat dissipation material having curability is used to form the heat dissipation material, a process of applying the heat dissipation material to a desired position before curing and then curing it is performed. However, even after applying the heat dissipation material, it is necessary to replace the parts in contact with the heat dissipation material in the product or change the position of the heat dissipation material and / or the parts, etc. However, if the curing of the heat dissipation material occurs quickly, the viscosity and hardness of the material also increase quickly, resulting in a problem of shortening the time available for replacement or position change, etc.

[0012] In addition, if the curing of the heat dissipation material occurs quickly, the time in which the material can be applied using the dispensing device or the injection device becomes shorter. Generally, in the process of applying the heat dissipation material, there may be a waiting time after the heat dissipation material is loaded into the dispensing device or the injection device, wherein if the curing of the heat dissipation material occurs quickly, the waiting time may not be properly ensured.

[0013] [Prior art literature]

[0014] [Patent Document]

[0015] (Patent Document 1) Korean Patent Publication No. 2016-0105354 Summary of the invention

[0016] Technical issues

[0017] The present application is intended to provide a curable composition, a thermal interface material (TIM) and its use. The thermal interface material can be a material formed by curing the curable composition. An object of the present application is that the curable composition or the thermal interface material, etc., exhibit low adhesion to a given adherend while exhibiting high thermal conductivity. In addition, in the purpose of the present application, it is included in the case of not using an adhesion regulating component such as a plasticizer or in a state where its use ratio is minimized to achieve low adhesion.

[0018] The present application also aims to ensure that the curable composition exhibits a precisely controlled curing rate and at the same time has excellent curability.

[0019] One object of the present application is to provide a product comprising a curable composition or a cured product thereof or a thermal interface material.

[0020] Technical Solution

[0021] In the physical properties mentioned in this specification, unless otherwise specified, when the measurement temperature affects the result, the relevant physical properties are physical properties measured at room temperature. The term room temperature is a natural temperature without warming or cooling, which generally means a temperature in the range of about 10°C to 30°C or a temperature of about 23°C or about 25°C. In addition, in this specification, unless otherwise specified, the unit of temperature is °C.

[0022] In the physical properties mentioned in this specification, unless otherwise specified, when the measurement pressure affects the result, the relevant physical properties are physical properties measured under normal pressure. The term normal pressure is a natural pressure without pressurization or decompression, which refers to an atmospheric pressure in the range of about 700 mmHg to 800 mmHg as normal pressure.

[0023] The present application relates to a resin composition. The term resin composition means a composition comprising a component known in the art as a resin, or a composition that does not contain a resin but contains a component that can form a resin through a curing reaction, etc. Therefore, in this specification, the scope of the term resin or resin component includes not only components commonly referred to as resins, but also components that can form resins through curing and / or polymerization reactions.

[0024] The resin composition may be a curable composition. The curable composition may be cured to form a thermal interface material (TIM). Therefore, in this specification, the cured product of the resin composition and the thermal interface material may refer to the same object.

[0025] When the resin composition of the present application is a curable composition, the resin composition may be a one-component composition or a two-component composition. The term one-component composition may refer to a resin composition in which the components participating in curing are contained in a state where they are in physical contact with each other, and the term two-component composition may refer to a resin composition in which at least some of the components participating in curing are physically separated to be separated and contained.

[0026] When the resin composition of the present application is a curable composition, the resin composition may be room temperature curing type, heat curing type, energy ray curing type and / or moisture curing type. The term room temperature curing type refers to a resin composition that can initiate and / or perform a curing reaction at room temperature; the term heat curing type refers to a resin composition that can initiate and / or perform a curing reaction by applying heat; the term energy ray curing type refers to a resin composition that can initiate and / or perform a curing reaction by irradiation with energy rays (e.g., ultraviolet rays or electron beams, etc.); the term moisture curing type refers to a resin composition that can initiate and / or perform a curing reaction in the presence of moisture.

[0027] The resin composition of the present application may be a solvent type or a solvent-free type. When considering application efficiency or environmental load, etc., a solvent-free type may be suitable.

[0028] The resin composition of the present application can be a polyurethane composition. In this case, the resin composition can include polyurethane, or can include a component capable of forming polyurethane. For example, the thermal interface material (which is a cured body of the resin composition) can include polyurethane. In an example, polyurethane can be formed by the reaction of the curable component described below with its curing agent.

[0029] The resin composition of the present application can show low adhesion to a specific adherend or form a solidified body that can show low adhesion. Such a resin composition can be a polyurethane composition. Polyurethane is known as an adhesive material that can show excellent adhesion to various adherends. Therefore, as a method for making the polyurethane composition show low adhesion to the adherend, a method of introducing a component such as a plasticizer that reduces adhesion is generally used. When such a component of a plasticizer is applied, the adhesion of the polyurethane material can be reduced, but there may be the following problem: the related component deteriorates other physical properties that can be ensured in the polyurethane, or it is dissolved from the material during the use process of the polyurethane material. However, in the present application, low adhesion can also be achieved for the polyurethane material without using an adhesion reducing component such as a plasticizer or minimizing the amount used. Therefore, in the present application, a material that solves the problem of high adhesion that is not required according to the purpose while utilizing the advantages of the polyurethane material can be provided.

[0030] The adhesion of the resin composition or its cured product to aluminum can be 1N / mm 2 The upper limit of the adhesion of the resin composition or its cured product to aluminum can also be 0.9 N / mm 2 , 0.8N / mm 2 , 0.7N / mm 2 , 0.6N / mm 2 , 0.5N / mm 2 , 0.4N / mm 2 , 0.3N / mm 2 , 0.2N / mm 2 , 0.1N / mm 2 , 0.15N / mm 2 , 0.09N / mm 2 , 0.08N / mm 2 , 0.07N / mm 2 , 0.06N / mm 2 , 0.04N / mm 2 or 0.03N / mm 2 The adhesion of the resin composition or its cured product to aluminum may be less than or equal to any of the above upper limits. In the present application, there is no particular restriction on the lower limit of the adhesion to aluminum. In one example, the adhesion to aluminum may be 0 N / mm2 or greater, or greater than 0N / mm 2 The resin composition may be a resin composition whose adhesive force to aluminum is substantially unmeasurable, or may be a resin composition capable of forming a cured body whose adhesive force to aluminum is substantially unmeasurable. Therefore, the adhesive force to aluminum may be greater than or equal to 0 N / mm 2 Or greater than 0N / mm 2 The adhesion of the resin composition or its cured product to aluminum can be measured in the manner described in Examples of this specification.

[0031] The adhesive force of the resin composition or its cured product to the polyester can be 100 gf / cm or less. In another example, the upper limit of the adhesive force of the resin composition or its cured product to the polyester can also 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 the polyester can be less than or equal to any one of the above upper limits. In the present application, there is no particular restriction on the lower limit of the adhesive force of the polyester. In one example, the lower limit of the adhesion of the resin composition or its solidified body to the polyester can be about 0gf / cm, 2gf / cm, 4gf / cm, 6gf / cm, 8gf / cm, 10gf / cm, 12gf / cm, 14gf / cm, 16gf / cm, 18gf / cm, or 20gf / cm. The resin composition or its solidified body may not substantially show adhesion to the polyester. The adhesion of the resin composition or its solidified body to the polyester can also be in the range of any one of the above lower limits to any one of the above upper limits. The adhesion of the resin composition or its solidified body to the polyester can be measured in the manner described in the embodiments of this specification.

[0032] Resin composition or its cured body can show excellent thermal conductivity.For example, the lower limit of the thermal conductivity of resin composition or its cured body can also be 1.2W / mk, 1.4W / mK, 1.6W / mK, 1.8W / mK, 2.0W / mK, 2.2W / mK, 2.4W / mK or more or about 2.6W / mK. Thermal conductivity can be greater than or equal to any one of the above lower limits. The upper limit of thermal conductivity is not particularly limited. For example, the upper limit of the thermal conductivity of resin composition or its cured body can also be 10W / mK, 9W / mK, 8W / mK, 7W / mK, 6W / mK, 5W / mK, 4W / mK or about 3W / mK. Thermal conductivity can also be in the range of any one of the above lower limits to any one of the above upper limits. The thermal conductivity of such resin composition or its cured body can be measured by the method disclosed in the embodiments described below.

[0033] The resin composition or its cured body can also show appropriate hardness. For example, if the hardness of the resin composition or its cured body is too high, there may be problems caused by excessive brittleness. In addition, by adjusting the hardness of the resin composition or its cured body, impact resistance and vibration resistance can be ensured, and the durability of the product can be ensured according to the application purpose. The upper limit of the hardness represented by Shore OO type of the resin composition or its cured body can be 150, 140, 130, 120, 110, 100, 90, 95 or 80. Shore OO type hardness can be less than or equal to any one of the above-mentioned upper limits. The lower limit of Shore OO type hardness can be 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85. Shore OO type hardness can be greater than or equal to any one of the above-mentioned lower limits. Shore OO type hardness can also be in the range of any one of the above-mentioned upper limits to any one of the above-mentioned lower limits. The hardness of such a resin composition or a cured product thereof can be measured by the method disclosed in Examples to be described below.

[0034] Resin combination or its cured body can also show suitable flexibility.For example, when the flexibility of resin combination or its cured body is adjusted to the desired level, the application can be greatly expanded.For example, the upper limit of the radius of curvature of resin combination or its cured body can be about 20,19,18,17,16,15,14,13,12,11,10,9 or 8.The radius of curvature can be less than or equal to any one of the above-mentioned upper limits.The lower limit of the radius of curvature can also be, for example, about 1,2,3,4,5,6,7,8,9,10 or 11.The radius of curvature can be greater than or equal to any one of the above-mentioned lower limits.The radius of curvature can also be in the range of any one of the above-mentioned upper limits to any one of the above-mentioned lower limits.The radius of curvature of such resin combination or its cured body can be measured by the method disclosed in the embodiment to be described below, and its unit is mm.

[0035] The resin composition of the present application may have insulating properties. That is, the resin composition may have insulating properties and / or form a cured body with insulating properties. For example, the dielectric breakdown voltage of the resin composition or its cured body measured according to ASTM D149 may be about 3kV / mm or greater, about 5kV / mm or greater, about 7kV / mm or greater, 10kV / mm or greater, 15kV / mm or greater, or 20kV / mm or greater. The higher the value of the dielectric breakdown voltage, the better the insulating properties, so the upper limit is not particularly limited, but considering the composition of the resin composition, the dielectric breakdown voltage may be about 50kV / mm or less, 45kV / mm or less, 40kV / mm or less, 35kV / mm or less, or about 30kV / mm or less. Such a dielectric breakdown voltage can be controlled by adjusting the insulating properties of the resin composition, which can be achieved, for example, by applying insulating fillers in the resin layer. Typically, in fillers, ceramic fillers are known to be components that can ensure insulating properties.

[0036] The resin composition or its cured product may have flame retardancy. For example, the resin composition or its cured product may show a V-0 grade in a UL94V test (vertical burning test). Therefore, stability may be ensured for fires and other accidents that are of concern according to the application of the resin composition.

[0037] The specific gravity of resin composition or its cured body can be 5 or less. In another example, the specific gravity can be 4.5 or less, 4 or less, 3.5 or less, or 3 or less. The resin layer showing a specific gravity within such a range is conducive to providing a lighter product. The lower limit of the specific gravity is not particularly limited. For example, the specific gravity can be about 1.5 or greater, or 2 or greater. In order to make the resin composition or its cured body show the specific gravity, the component added to the resin layer can be adjusted. For example, when adding filler, a filler that can ensure the desired properties (for example, thermal conductivity) even at the lowest possible specific gravity can be used, that is, a filler with a low specific gravity or a method of applying a surface-treated filler, etc. can be used.

[0038] The resin composition may have a low shrinkage during or after curing. Thus, peeling or void generation, etc., which may occur during the application process, can be prevented. The shrinkage can be appropriately adjusted within a range that can exhibit the above-mentioned effects, which may be, for example, less than 5%, less than 3%, or less than about 1%. Since the lower the shrinkage value, the more advantageous it is, the lower limit is not particularly limited.

[0039] Resin combination or its cured body can have low coefficient of thermal expansion (coefficient of thermal expansion, CTE).Thus, it is possible to prevent peeling or gap generation etc. that may occur during application or use process.The coefficient of thermal expansion can be appropriately adjusted in the range that can show the above-mentioned effect, and it can be, for example, less than 300ppm / K, less than 250ppm / K, less than 200ppm / K, less than 150ppm / K or less than about 100ppm / K.Because the value of the coefficient of thermal expansion is lower, it can be more advantageous, so the lower limit is not particularly limited.

[0040] In the resin composition or its cured body, the 5% weight loss temperature in thermogravimetric analysis (TGA) can be 400°C or higher, or the 800°C residue can be 70% by weight or more. With such characteristics, the stability at high temperatures can be further improved. In another example, the 800°C residue can be about 75% by weight or more, about 80% by weight or more, about 85% by weight or more, or about 90% by weight or more. In another example, the 800°C residue can be about 99% by weight or less. Thermogravimetric analysis (TGA) can be performed at 60 cm 3 The results of thermogravimetric analysis (TGA) can also be achieved by controlling the composition of the resin composition. For example, the 800°C residual amount is generally affected by the type or ratio of the filler included in the resin composition, and when an excessive amount of filler is included, the residual amount increases.

[0041] The resin composition of the present application may include a curable component. The term curable component means a component comprising one or more compounds containing a functional group that can participate in a curing reaction. In an example, the functional group that can participate in a curing reaction can be a hydroxyl group. Therefore, the curable component may include a reactive compound with a hydroxyl group. Here, it means that because the reactive compound has a hydroxyl group, it is a compound that can participate in a curing reaction. Such a reactive compound may be a monomolecular compound, an oligomeric compound, or a polymer compound.

[0042] The reactive compound having a hydroxyl group may be a monofunctional compound or a polyfunctional compound. The term monofunctional compound means a reactive compound containing one hydroxyl group per molecule, and the term polyfunctional compound means a reactive compound containing two or more hydroxyl groups per molecule.

[0043] In addition, the reactive compound having a hydroxyl group may be an oil-modified compound or a non-oil-modified compound described below. The oil-modified compound may be a monofunctional compound or a polyfunctional compound, and the non-oil-modified compound may also be a monofunctional compound or a polyfunctional compound.

[0044] In the present specification, a polyfunctional compound may be referred to as a polyol compound. The number of hydroxyl groups contained in the polyfunctional compound (polyol compound) is not particularly limited. In one example, the lower limit of the number of hydroxyl groups contained in the polyfunctional compound (polyol compound) may be 2 or 3 per molecule. The number of hydroxyl groups contained in the polyfunctional compound (polyol compound) may be greater than or equal to any one of the above lower limits. The upper limit of the number of hydroxyl groups contained in the polyfunctional compound (polyol compound) may also be about 10, 9, 8, 7, 6, 5, 4, 3 or 2 per molecule. The number of hydroxyl groups contained in the polyfunctional compound (polyol compound) may be less than or equal to any one of the above upper limits. The number of hydroxyl groups contained in the polyfunctional compound (polyol compound) may also be in the range from any one of the above lower limits to any one of the above upper limits. The number of hydroxyl groups contained in the polyol compound can be increased by 1 H NMR, where the number of hydroxyl groups can be based on 1 The peaks in the 3 ppm to 4 ppm region of HNMR were used for determination.

[0045] The reactive compound may be an oil-modified compound. The term oil-modified compound means a compound containing a hydroxyl group and containing a linear or branched hydrocarbon group having three or more carbon atoms at the terminal. Therefore, a reactive compound without any linear or branched hydrocarbon group having three or more carbon atoms at the terminal may be referred to herein as a non-oil-modified compound. Whether the reactive compound contains a hydrocarbon group can be determined by 1 H NMR, where the presence and number of hydrocarbon groups can be determined based on 1 The oil-modified compound can be determined by the presence of a peak in the region of 4 ppm to 5 ppm in H NMR. When the oil-modified compound is applied to form a polyurethane material, low adhesion to a specific material can be ensured while not using an adhesion-reducing component such as a plasticizer or minimizing the amount used.

[0046] The lower limit of the number of carbon atoms of the linear or branched hydrocarbon group contained at the end of the oil-modified compound can be about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17. The number of carbon atoms can be greater than or equal to any one of the above lower limits. The upper limit of the number of carbon atoms can also 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 can be less than or equal to any one of the above upper limits. The number of carbon atoms can be in the range of any of the above lower limits to any of the above upper limits.

[0047] The linear or branched hydrocarbon group may or may not contain double bonds. In the case of containing double bonds, such double bonds may be conjugated double bonds or cis double bonds.

[0048] The specific type of alkyl can be exemplified as alkyl, alkenyl or alkynyl. In one example, alkyl can be connected to alcohol compound via carbonyl or carbonyloxy, in which case alkyl can be alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy or alkynylcarbonyloxy. Here, the number of carbon atoms in alkyl, alkenyl or alkynyl can also be greater than or equal to any one of the lower limits of the number of carbon atoms in the above-mentioned linear or branched alkyl, less than or equal to any one of the upper limits of the number of carbon atoms in the above-mentioned linear or branched alkyl, or in the range of any one of the lower limits of the number of carbon atoms in the above-mentioned linear or branched alkyl to any one of the upper limits of the number of carbon atoms in the above-mentioned linear or branched alkyl.

[0049] The alkyl, alkenyl or alkynyl group may be linear or branched, and may be optionally substituted with a substituent. When a substituent is present, the type of the substituent is not particularly limited, and for example, a halogen atom (eg, fluorine) can be exemplified as a substituent.

[0050] In one example, a hydrocarbon group may be included in the substituent of Formula 1 below.

[0051] [Formula 1]

[0052]

[0053] In Formula 1, R is a linear or branched hydrocarbon group.

[0054] In Formula 1, the symbol * means that the relevant part is connected to the polyol compound. Therefore, the oxygen atom in the substituent of Formula 1 may be connected to the polyol compound.

[0055] The specific types of the hydrocarbon group as R in Formula 1 are as described above. Therefore, the contents regarding the carbon number, type, form and substituent of the above hydrocarbon group can be applied in the same manner as above.

[0056] The number of hydrocarbon groups contained in the reactive compound is not particularly limited. For example, the lower limit of the number of hydrocarbon groups contained in the reactive compound may be 1 or 2 per molecule of the compound. The upper limit of the number of hydrocarbon groups contained in the reactive compound may also be about 10, 9, 8, 7, 6, 5, 4, 3, or 2 per molecule of the compound. The number of hydrocarbon groups may also be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range from any of the above lower limits to any of the above upper limits.

[0057] The oil-modifying compound may have various forms as long as it contains a hydroxyl group and a hydrocarbon group.

[0058] In an example, the oil-modified compound can be a compound of at least some forms of hydroxyl and / or alkyl replacement in the hydrogen atom of hydrocarbon compounds such as alkanes, alkene or alkynes. The carbon number in hydrocarbon compounds such as alkanes, alkene or alkynes can be for example 1 to 20, 1 to 16, 1 to 8 or 4 to 6. Such hydrocarbon compounds such as alkanes, alkene or alkynes can be linear, branched or cyclic. In addition, hydroxyl and / or alkyl in alkanes, alkene or alkynes can replace on the same carbon atom, or can also replace on different carbon atoms.

[0059] In another example, the reactive compound may be a compound having a polyester skeleton or a polyether skeleton. In this case, the reactive compound may be an oligomer compound or a polymer compound.

[0060] In one example, when the reactive compound having a polyester skeleton is a polyol compound, the relevant compound is a so-called polyester polyol, and may be a polyol having a structure in which a hydrocarbon group is linked to the polyester polyol.

[0061] Furthermore, when the reactive compound having a polyether skeleton is a polyol compound, the compound in question is a so-called polyether polyol, and may be a polyol having a structure in which a hydrocarbon group is linked to the polyether polyol.

[0062] In one example, the polyester skeleton may be a so-called polycaprolactone skeleton, and the polyether skeleton may be a so-called polyalkylene skeleton.

[0063] In one example, the polyester backbone may be a backbone having a repeating unit represented by Formula 2 below.

[0064] [Formula 2]

[0065]

[0066] In Formula 2, X1 and X2 are each independently a single bond or an oxygen atom, L1 may be an alkylene group or an alkylidene group, and n is an arbitrary number.

[0067] In the present specification, the term single bond means the situation where no atom is present at the relevant site.

[0068] In Formula 2, in one example, the alkylene group may 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, which may be linear or branched.

[0069] In Formula 2, in one example, the alkylidene group 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.

[0070] In the present specification, both alkylene and alkylidene mean a divalent substituent formed by leaving two hydrogen atoms in an alkane. Alkylene and alkylidene are different from each other in that alkylene is a divalent substituent formed by leaving two hydrogen atoms from different carbon atoms of an alkane, while alkylidene is a divalent substituent formed by leaving two hydrogen atoms from one carbon atom of an alkane.

[0071] In one example, the polyester backbone may be a polycaprolactone backbone, in which case L1 of the above Formula 2 may be a linear alkylene group having 5 carbon atoms or a linear alkylidene group having 5 carbon atoms.

[0072] In Formula 2, n is an arbitrary number representing the number of repeating units. The lower limit of the above 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 above n may also be greater than or equal to any lower limit of the above lower limits, less than or equal to any upper limit of the above upper limits, or within the range of any lower limit of the above lower limits to any upper limit of the above upper limits.

[0073] The skeleton of formula 2 can be a so-called carboxylic acid polyol skeleton or a caprolactone polyol skeleton. Such a skeleton can be formed in a known manner, for example, the skeleton of a carboxylic acid polyol can be formed by reacting a component comprising a carboxylic acid with a polyol (e.g., diol or triol, etc.), and the skeleton of a caprolactone polyol can be formed by reacting a component comprising caprolactone with a polyol (e.g., diol or triol, etc.). The carboxylic acid can be a dicarboxylic acid.

[0074] In the oil-modified compound having the skeleton of Formula 2, a hydroxyl group or the above-mentioned hydrocarbon group may be present at the terminal of the skeleton of Formula 2.

[0075] In this case, the skeleton of the above Formula 2 can be represented by the following Formula 3.

[0076] [Formula 3]

[0077]

[0078] In Formula 3, X1, X2, L1 and n are as defined in Formula 2, and R1 may be a hydroxyl group or a substituent of the following Formula 4.

[0079] [Formula 4]

[0080]

[0081] In Formula 4, X3 is a single bond or an oxygen atom, and R is the same as R in Formula 1 above.

[0082] When R1 in Formula 3 is a hydroxyl group, X1 may be a single bond, and X2 may be an oxygen atom; when R1 is a substituent of the above Formula 4, either X1 or X3 may be a single bond, and the other may be an oxygen atom.

[0083] In the oil-modified compound, the lower limit of the number of the skeletons of Formula 2 or Formula 3 above may be about 1 or 2, and the upper limit may be about 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of the skeletons may also be greater than or equal to any of the lower limits, less than or equal to any of the upper limits, or within the range from any of the lower limits to any of the upper limits.

[0084] The oil-modified compound having a polyester backbone may have a linear or branched structure.

[0085] Here, the linear structure is a structure in which there is a main chain comprising a skeleton of Formula 2 or Formula 3 above and no other polymer chain is connected to the main chain, and the branched structure may be in the form of a chain comprising a skeleton of Formula 2 or Formula 3 above as a side chain bonded to the main chain comprising the skeleton of Formula 2 or Formula 3 above. Here, in the branched structure, the number of chains comprising the skeleton of Formula 2 or Formula 3 above connected as side chains may be, for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1.

[0086] In one example, the oil-modified compound having a polyester skeleton may be a compound in which at least some of the hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene, or an alkyne are substituted with hydroxyl groups and / or the skeleton of the above formula 3. The number of carbon atoms in the hydrocarbon compound such as an alkane, an alkene, or an alkyne may be, for example, 1 to 20, 1 to 16, 1 to 8, or 4 to 6.

[0087] Such hydrocarbon compounds such as alkanes, alkenes or alkynes can be linear, branched, or cyclic. In addition, the hydroxyl group and / or the skeleton of formula 3 can be substituted on the same carbon atom in the alkane, alkene or alkyne, or can also be substituted on different carbon atoms.

[0088] In one example, the polyether skeleton may be a skeleton having a repeating unit of Formula 5 below.

[0089] [Formula 5]

[0090]

[0091] In Formula 5, X4 and X5 are each independently a single bond or an oxygen atom, L2 may be an alkylene group or an alkylidene group, and m is an arbitrary number.

[0092] In Formula 5, in one example, the alkylene group may be an alkylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, which may be linear or branched.

[0093] In Formula 5, in one example, the alkylidene group may be an alkylidene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, which may be linear or branched.

[0094] The meanings of the alkylene group and the alkylidene group are as defined above.

[0095] In Formula 5, m is an arbitrary number representing the number of repeating units, which may be a number in the range of 1 to 25, for example.

[0096] In the oil-modified compound having the skeleton of Formula 5, a hydroxyl group or the above-mentioned hydrocarbon group may be present at the terminal of the skeleton of Formula 5 above.

[0097] In this case, the skeleton of Formula 5 can be represented by the following Formula 6.

[0098] [Formula 6]

[0099]

[0100] In Formula 6, X4, X5, L2 and m are as defined in Formula 5, and R2 may be a hydroxyl group or a substituent of the following Formula 7.

[0101] [Formula 7]

[0102]

[0103] In Formula 7, X6 is a single bond or an oxygen atom, and R is the same as R in Formula 1 above.

[0104] When R2 in Formula 6 is a hydroxyl group, X4 is a single bond; when R2 is a substituent of Formula 7, either X4 or X6 is a single bond, and the other is an oxygen atom.

[0105] The oil-modified compound may contain one or more, or two or more skeletons of the above formula 5 or 6. The skeleton of the above formula 5 or 6 may be contained in the polyol compound in an amount of 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less.

[0106] The polyol compound having a polyether skeleton may have a linear or branched structure.

[0107] Here, the linear structure may be a structure in which a main chain including a skeleton of Formula 5 or Formula 6 is present and no other polymer chain is connected to the main chain, and the branched structure may be in the form of a chain including a skeleton of Formula 5 or Formula 6 as a side chain bonded to the main chain including a skeleton of Formula 5 or Formula 6. Here, in the branched structure, the number of chains including a skeleton of Formula 5 or Formula 6 connected as a side chain may be, for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1.

[0108] In one example, the oil-modified compound having a polyether skeleton may be a compound in which at least some of the hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene, or an alkyne are substituted with hydroxyl groups and / or the skeleton of the above formula 5. The number of carbon atoms in the hydrocarbon compound such as an alkane, an alkene, or an alkyne may be, for example, 1 to 20, 1 to 16, 1 to 8, or 4 to 6.

[0109] Such hydrocarbon compounds such as alkanes, alkenes or alkynes can be linear, branched, or cyclic. In addition, the hydroxyl group and / or the skeleton of formula 5 can be substituted on the same carbon atom in the alkane, alkene or alkyne, or can also be substituted on different carbon atoms.

[0110] When the above-mentioned oil-modifying compound is an oligomer compound or a polymer compound, the relevant compound may have a molecular weight at an appropriate level.

[0111] For example, the lower limit of the weight average molecular weight of the oligomer oil modified compound or the polymer oil modified compound can 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 thereof can also be about 3,000 g / mol, 2500 g / mol, 2000 g / mol, 1500 g / mol, 1000 g / mol, or 900 g / mol. The weight average molecular weight can also be greater than or equal to any one of the above lower limits, less than or equal to any one of the above upper limits, or within the range of any one of the above lower limits to any one of the above upper limits.

[0112] By applying the oil-modifying compound as described above, desired physical properties can be more effectively ensured.

[0113] The oil-modified compound can be present in the resin combination with an appropriate ratio. For example, the lower limit of the ratio of the oil-modified compound in the resin combination can be about 50 wt %, 55 wt %, 60 wt %, 65 wt %, 70 wt %, 75 wt %, 80 wt % or 85 wt %, and its upper limit can be about 95 wt % or 90 wt %. The ratio can also be greater than or equal to any one of the above-mentioned lower limit, less than or equal to any one of the above-mentioned upper limit, or in the scope of any one of the above-mentioned lower limit to any one of the above-mentioned upper limit.

[0114] When the resin composition is a one-component type, the content of the oil-modified compound is the content in the relevant one-component composition, and when the resin composition is a two-component composition, it is the content in the part where the oil-modified compound is present. For example, when the two-component composition comprises a physically separated main part and a curing agent part and the oil-modified compound is contained in the main part, the content of the oil-modified compound can be the content based on the total weight of the main part. In addition, when the resin composition comprises a solvent and / or a filler, the content is the content based on the weight excluding the content of the solvent and the filler.

[0115] In another example, when resin combination includes the filler component to be described below, relative to 100 weight parts of filler components, the lower limit of the weight ratio of oil-modified compound can be 1 weight part, 2 weight parts, 3 weight parts, 4 weight parts, 5 weight parts, 6 weight parts, 7 weight parts, 8 weight parts, 9 weight parts or about 10 weight parts, and its upper limit can be 30 weight parts, 28 weight parts, 26 weight parts, 24 weight parts, 22 weight parts, 20 weight parts, 18 weight parts, 16 weight parts, 14 weight parts or about 12 weight parts. The ratio can also be greater than or equal to any one of the above-mentioned lower limit, less than or equal to any one of the above-mentioned upper limit, or in the scope of any one of the above-mentioned lower limit to any one of the above-mentioned upper limit.

[0116] When the resin composition is a one-component type, the ratio of the filler component is a ratio relative to 100 parts by weight of the total filler components contained in the relevant resin composition, and when the resin composition is a two-component type, the ratio of the filler component is a ratio relative to 100 parts by weight of the total filler components present in the part (main part or curing agent part) containing the oil-modified polyol.

[0117] The oil-modified compound can be synthesized by a known synthesis method. That is, the compound can be prepared by reacting a compound capable of introducing a hydrocarbon group corresponding to the oil-modified part with a known polyol compound or alcohol compound. Here, the polyol compound is a compound having two or more hydroxyl groups per molecule, and the alcohol compound is a compound having one hydroxyl group per molecule. Here, the compound capable of introducing a hydrocarbon group can be exemplified by saturated fatty acids or unsaturated fatty acids, specifically, butyric acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, linoleic acid or oleic acid, but are not limited thereto.

[0118] Furthermore, the type of the polyol compound or alcohol compound to be reacted with the saturated fatty acid or unsaturated fatty acid is not particularly limited, and for example, an appropriate type of general reactive compound to be described below may be applied, but is not limited thereto.

[0119] The reactive compound with hydroxyl group can also include reactive compounds different from oil-modified compounds. In this case, the reactive compound does not include the above-mentioned hydrocarbon radical (i.e., a linear or branched hydrocarbon radical with 3 or more carbon atoms). For convenience, in this specification, such reactive compounds can be referred to as non-oil-modified compounds.

[0120] The non-oil modified compound also contains one or more hydroxyl groups per molecule. The lower limit of the number of hydroxyl groups contained in the non-oil modified compound can be about 1, 2, or 3, and the upper limit thereof can be about 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of hydroxyl groups can also be greater than or equal to any one of the above-mentioned lower limits, less than or equal to any one of the above-mentioned upper limits, or in the range of any one of the above-mentioned lower limits to any one of the above-mentioned upper limits.

[0121] The non-oil modified compound may also be a monomolecular compound, an oligomeric compound, or a polymeric compound.

[0122] The non-oil modifying compound can have various forms.

[0123] In one example, the non-oil modified compound may be a polyester polyol. As the polyester polyol, for example, a so-called carboxylic acid polyol or a caprolactone polyol may be used.

[0124] In one example, the polyester polyol may have a skeleton having a repeating unit represented by Formula 8 below.

[0125] [Formula 8]

[0126]

[0127] In Formula 8, X7 and X8 are each independently a single bond or an oxygen atom, L3 may be an alkylene group or an alkylidene group, and p is an arbitrary number.

[0128] In Formula 8, in one example, the alkylidene group 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.

[0129] In Formula 8, in one example, the alkylene group may 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, which may be linear or branched.

[0130] When the polyester polyol is polycaprolactone polyol, L3 of the above formula 8 may be a linear alkylene group having 5 carbon atoms.

[0131] Furthermore, in the above Formula 8, p is an arbitrary number representing the number of repeating units, which may be a number in the range of 1 to 25, for example.

[0132] The polyester polyol having the skeleton of the above formula 8 can be a so-called carboxylic acid polyol or a caprolactone polyol. Such a polyol compound can be formed by a known method, for example, a carboxylic acid polyol can be formed by reacting a component containing a carboxylic acid with a polyol (e.g., a diol or a triol, etc.), and a caprolactone polyol can be formed by reacting a component containing caprolactone with a polyol (e.g., a diol or a triol, etc.). The carboxylic acid can be a dicarboxylic acid.

[0133] In the polyol compound having the skeleton of the above Formula 8, a hydroxyl group may be present at the terminal of the skeleton of the above Formula 8 or at another site of the polyester polyol.

[0134] When the non-oil modified compound includes the skeleton of Formula 8 above, the lower limit of the number of the relevant skeletons can be about 1, or 2, and the upper limit thereof can also be about 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1. The number of the skeletons can also be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range of any of the above lower limits to any of the above upper limits.

[0135] The polyol compound having a polyester skeleton may have a linear or branched structure.

[0136] Here, the linear structure may be a structure in which a main chain including a skeleton of the above formula 8 is present and no other polymer chain is connected to the main chain, and the branched structure may be in the form in which a chain including a skeleton of the above formula 8 as a side chain is bonded to the main chain including the skeleton of the above formula 8. In the branched structure, the number of chains including the skeleton of the above formula 8 connected as side chains may be, for example, 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1.

[0137] In another example, polyols with polycaprolactone polyol units or alkanediol units, polyol units and dicarboxylic acid units can also be used as non-oil modified compounds. Such polyols can be a mixture of the above polycaprolactone polyol units or alkanediols, polyols and dicarboxylic acids, or a reaction product thereof. At this point, alkanediols can be exemplified as diol compounds with 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. In addition, polyol units can be exemplified as alkanes or polycarbons with 1 to 20 carbon atoms, 4 to 20 carbon atoms, 4 to 16 carbon atoms, or 4 to 12 carbon atoms substituted by 3 to 10, 3 to 9, 3 to 8, 3 to 7, 3 to 6, 3 to 5, or 3 to 4 hydroxyl groups, such as trimethylolpropane. In addition, the dicarboxylic acid can be exemplified by adipic acid, terephthalic acid, isophthalic acid, or sebacic acid. Such a polyol compound is known, for example, as Kuraray's product name 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.

[0138] As such a non-oil modifying compound, a polyol having a weight average molecular weight in the range of 100 g / mol to 5,000 g / mol may be used. By using such a polyol, the desired effect may be more effectively achieved.

[0139] The curable component in the curable composition of the present application may be composed of any one of the above-mentioned reactive compounds, or may be composed of a mixture of two or more of the foregoing.

[0140] In one example, the curable component may include a monofunctional compound (which may be referred to as a first reactive compound) and a polyfunctional compound (which may be referred to as a second reactive compound) among the above-mentioned reactive compounds. At this time, the monofunctional compound and the polyfunctional compound may each independently be an oil-modified compound or a non-oil-modified compound.

[0141] In this case, the lower limit of the weight ratio of the monofunctional compound relative to 100 parts by weight of the polyfunctional compound can be, for example, 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 about 95 parts by weight, and the upper limit thereof can be, for example, 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 about 105 parts by weight. The ratio can also be greater than or equal to any one of the above lower limits, less than or equal to any one of the above upper limits, or within the range of any one of the above lower limits to any one of the above upper limits.

[0142] In the above case, the curable component may include a reactive compound having two hydroxyl groups (which may be referred to as a third reactive compound) and a reactive compound having three or more hydroxyl groups (which may be referred to as a fourth reactive compound) as the second reactive compound. The upper limit of the number of hydroxyl groups contained in the fourth reactive compound may also be about 10, 9, 8, 7, 6, 5, 4, or 3 per molecule. The number of hydroxyl groups in the fourth reactive compound may be 3 or more while being less than or equal to any of the above upper limits.

[0143] In this case, the lower limit of the weight ratio of the fourth reactive compound relative to 100 parts by weight of the third reactive compound may be, for example, 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 about 10 parts by weight, and the upper limit thereof 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 about 12 parts by weight. The ratio may also be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range from any of the above lower limits to any of the above upper limits.

[0144] As described above, the first to fourth reactive compounds may each independently be an oil-modified compound or a non-oil-modified compound.

[0145] In appropriate examples, the first reactive compound and the third reactive compound among the first to fourth reactive compounds may be oil-modified compounds.

[0146] In this case, the fourth reactive compound may be an oil-modified compound or a non-oil-modified compound, and in appropriate examples, it may be a non-oil-modified compound. As the non-oil-modified compound, for example, a compound comprising a polycaprolactone polyol unit or an alkanediol unit; a polyol unit and a dicarboxylic acid unit as described above may be used.

[0147] The resin composition may contain, for example, a curing agent that reacts with the curable component as an additional component.

[0148] As curing agent, various types can be applied, but when the resin composition is a polyurethane composition, polyisocyanates (also referred to as polyisocyanate compounds) can be applied as curing agent. The term polyisocyanate means a compound with two or more isocyanate groups. The lower limit of the number of isocyanate groups in the polyisocyanate can be about 2 or 3, and the upper limit can be about 10, 9, 8, 7, 6, 5, 4, 3 or 2. The number of isocyanate groups can also be greater than or equal to any one of the above-mentioned lower limit, less than or equal to any one of the above-mentioned upper limit, or in the range of any one of the above-mentioned lower limit to any one of the above-mentioned upper limit.

[0149] The type of polyisocyanate used as the curing agent is not particularly limited, but non-aromatic polyisocyanate containing no aromatic group may be used in order to ensure desired physical properties.

[0150] In addition, as the polyisocyanate, if necessary, a polyisocyanate having difunctionality and a polyisocyanate having trifunctionality or more may also be used together. Here, difunctionality means that the compound contains two isocyanate groups, and trifunctionality means that the compound contains three or more isocyanate groups.

[0151] As the polyisocyanate compound, for example, aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate, methyl norbornane diisocyanate (norbornane diisocyanate methyl), ethylene diisocyanate, propylene diisocyanate, or tetramethylene diisocyanate can be used; alicyclic polyisocyanates such as trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis (isocyanate methyl) cyclohexane diisocyanate, or dicyclohexylmethane diisocyanate; or one or more of the foregoing polyisocyanates modified with carbodiimide or polyisocyanates modified with isocyanurate; and the like. In addition, as the polyisocyanate, the addition reaction product of the diisocyanate as described above and a polyol (e.g., trimethylolpropane, etc.) can also be used. In addition, a mixture of two or more of the compounds listed above can be used.

[0152] The application ratio of the polyisocyanate may be adjusted in consideration of the number of hydroxyl groups present in the curable component included in the resin composition and the physical properties after curing.

[0153] For example, the polyisocyanate may be included in the resin composition such that an equivalent ratio (OH / NCO) of the number of hydroxyl groups (OH) present in the curable component to the number of isocyanate groups (NCO) present in the polyisocyanate may be within a predetermined range.

[0154] Methods for calculating the equivalent ratio (OH / NCO) are known.

[0155] For example, if the resin composition is a two-component type, the curable component is contained in the main part, and the polyisocyanate is contained in the curing agent part, the equivalent ratio OH / NCO can be calculated according to the following General Formula 1.

[0156] [General formula 1]

[0157]

[0158] In general formula 1, E is the equivalent ratio OH / NCO, D m is the density of the main part, D c is the density of the curing agent part, A is obtained according to the following general formula 2, B is obtained according to the following general formula 3, and D NCO is the Dalton mass of the isocyanate group, which is 42 Da, and D OH is the Dalton mass of the hydroxyl group, which is 17D a .

[0159] [General formula 2]

[0160] A=∑(W OH ×OH ％ )

[0161] In general formula 2, W OH is the weight ratio of the reactive compound present in the main part, and OH% is the weight ratio W OH The ratio of hydroxyl groups contained in the reactive compound.

[0162] [General formula 3]

[0163] B=∑(W NCO ×N CO％ )

[0164] In general formula 3, W NCO is the weight ratio of the polyisocyanate present in the curing agent part, and NCO% is the weight ratio W NCO The ratio of isocyanate groups contained in the polyisocyanate.

[0165] Here, W OH is the weight % in the main part of each reactive compound present in the main part (based on the total weight of the main part), and the OH% of the relevant compound is the % of hydroxyl groups contained in 1 mole of each reactive compound, which is obtained by dividing the product of the number of moles of hydroxyl groups contained in a single reactive compound and the molar mass of the hydroxyl groups by the molar mass of the single reactive compound and then multiplying by 100.

[0166] Here, W NCO is the weight % in the curing agent part (based on the total weight of the curing agent part) of each polyisocyanate present in the curing agent part, and the NCO % of the relevant compound is the % of the NCO group contained in 1 mol of each polyisocyanate, which is obtained by dividing the product of the number of moles of NCO groups contained in a single polyisocyanate and the molar mass of the NCO group by the molar mass of the single polyisocyanate and then multiplying by 100.

[0167] In general formula 1, the Dalton mass is a constant.

[0168] The lower limit of the equivalent ratio (OH / NCO) can 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 thereof can also 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 equivalence ratio may also be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range from any of the above lower limits to any of the above upper limits.

[0169] The resin composition may further include a filler component. The term filler component means a component composed of a filler, that is, a component containing only a filler.

[0170] In one example, the filler component can include two or more fillers with different average particle sizes. In one example, the filler component can include three or more fillers with different average particle sizes, or can be composed of three to six, three to five, three to four, or three fillers with different average particle sizes. That is, in one example, the filler component can also only include three to six, three to five, three to four, or three fillers with different average particle sizes.

[0171] In another example, the filler component can show at least two peaks in the volume curve of the particle size distribution measured using laser diffraction. In one example, the filler component can show three or more peaks in the volume curve of the particle size distribution, or can show three to six, three to five, three to four, or three peaks. For example, within the range of the filler component showing three peaks, filler components showing one, two, or four or more peaks are not included.

[0172] The average particle size of the filler in the present application means the particle size at which the volume accumulation becomes 50% in the volume curve of the particle size distribution measured by laser diffraction, which can also be referred to as the median diameter. That is, in the present application, the particle size distribution is obtained based on the volume by laser diffraction, and the particle size at the point where the cumulative value becomes 50% in the cumulative curve with a total volume of 100% is set as the average particle size. In another example, such an average particle size can be referred to as the median particle size or D50 particle size.

[0173] Therefore, here, two fillers having different average particle sizes may mean fillers having different particle sizes at a point where a cumulative value becomes 50% in a volume curve of particle size distribution.

[0174] When two or more fillers having different average particle sizes are generally mixed to form a filler component, as many peaks as the types of mixed fillers appear on the volume curve of particle size distribution measured using laser diffraction for the filler component. Thus, for example, when three fillers having different average particle sizes are mixed to constitute a filler component, the volume curve of particle size distribution measured using laser diffraction for the filler component shows three peaks.

[0175] The filler component of the resin composition of the present application may be a thermally conductive filler component. The term thermally conductive filler component means a filler component that plays a role in making the resin composition or its cured body exhibit the above-mentioned thermal conductivity.

[0176] In one example, the filler component may include at least a first filler having an average particle size of 60 to 200 μm, a second filler having an average particle size ranging from 10 to 30 μm, and a third filler having an average particle size of 5 μm or less.

[0177] As another example, the first filler can have an average particle size of about 62 μm or more, 64 μm or more, 66 μm or more, or about 68 μm or more, and / or about 195 μm or less, 190 μm or less, 185 μm or less, 180 μm or less, 175 μm or less, 170 μm or less, 165 μm or less, 160 μm or less, 155 μm or less, 150 μm or less, 145 μm or less, 140 μm or less, 135 μm or less, 130 μm or less, 125 μm or less, about 120 μm or less, 115 μm or less, 110 μm or less, 105 μm or less, 100 μm or less, 95 μm or less, 90 μm or less, 85 μm or less, 80 μm or less, or about 75 μm or less.

[0178] As another example, the average particle size of the second filler can be 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.

[0179] As another example, the average particle size of the third filler can be about 0.01 μm or greater, 0.1 μm or greater, about 0.5 μm or greater, 1 μm or greater, 1.5 μm or greater, or 2 μm or greater, and / or about 5 μm or less, 4.5 μm or less, about 4 μm or less, 3.5 μm or less, 3 μm or less, 2.5 μm or less, or 2 μm or less.

[0180] The ratio (D1 / D3) of the average particle size (D1) of the first filler to the average particle size (D3) of the third filler in the filler component may be in the range of 25 to 300.

[0181] In one example, when the filler component includes two or more fillers having different average particle sizes, the third filler may be a filler having the smallest average particle size among the fillers included in the filler component, and when the filler component includes two or more fillers having different average particle sizes, the first filler may be a filler having the largest average particle size among the fillers included in the filler component. In such a state, the particle size ratio may be satisfied.

[0182] In another example, 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 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.

[0183] 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 another example, 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 also 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.

[0184] As fillers, for example, ceramic materials such as aluminum oxide (aluminum oxide: 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 conducive to satisfying the thermal conductivity within the above range, and in addition, the above-mentioned insulation characteristics, etc. can also be satisfied by applying ceramic fillers.

[0185] The upper limit of the ratio of filler component in resin combination can be 95 weight %, 94.5 weight %, 94 weight %, 93.5 weight %, 93 weight %, 92.5 weight %, 92 weight %, 91.5 weight %, 91 weight %, 90.5 weight %, 90.0 weight %, 89.5 weight % or 89.0 weight % or so, and its lower limit can be 70 weight %, 71 weight %, 72 weight %, 73 weight %, 74 weight %, about 75 weight %, 76 weight %, 77 weight %, 78 weight %, 79 weight %, 80 weight %, 81 weight %, 82 weight %, 83 weight %, 84 weight %, 85 weight %, 86 weight %, 87 weight % or 88 weight % or so.Described ratio can also be greater than or equal to any one in the above-mentioned lower limit, be less than or equal to any one in the above-mentioned upper limit, or in the scope of any one in the above-mentioned lower limit to any one in the above-mentioned upper limit.

[0186] The lower limit of the ratio of the filler component relative to 100 parts by weight of the total weight of the curable component or the reactive compounds 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 also be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range from any of the above lower limits to any of the above upper limits.

[0187] When the resin composition is a one-component composition, the content of the filler component may be a ratio based on the total weight of the relevant resin composition, and in the case of a two-component resin composition, the content of the filler component may be a ratio based on the combined weight of the main part and the curing agent part of the two-component composition, or may be a ratio based on the total weight of the main part or the curing agent part alone.

[0188] When the resin composition is composed of a two-component composition, it may be appropriate that the filler component applied as a filler component to the final cured body is divided into substantially equal amounts and introduced into the main part and the curing agent part, respectively.

[0189] If necessary, the filler component may include various types of fillers, for example, carbon fillers (eg, graphite), fumed silica, or clay, etc., in addition to thermally conductive fillers.

[0190] The resin composition may further contain necessary components in addition to the above-mentioned components.

[0191] In one example, the resin composition may further include a plasticizer. As described above, in the present application, low adhesion to a specific material can be ensured without using a plasticizer, but a small amount of a plasticizer may be used if necessary.

[0192] There is no particular limitation on the type of plasticizer that can be applied, for example, a phthalate-based plasticizer such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), diisononyl phthalate (DINP) or polyethylene terephthalate (PET); an adipate-based plasticizer such as dioctyl adipate (DOA) or diisononyl adipate (DINA); a fatty acid-based plasticizer; a phosphoric acid-based plasticizer; or a polyester-based plasticizer; and the like can be applied.

[0193] When comprising plasticizer, ratio can be adjusted according to purpose.For example, relative to the gross weight of 100 weight portions of the reactive compound present in curable component or curable component, the lower limit of the ratio of plasticizer can be 0.5 weight portion, 1 weight portion, 1.5 weight portions, 2 weight portions, 2.5 weight portions, 3 weight portions, 3.5 weight portions, 4 weight portions, 4.5 weight portions, 5 weight portions, 5.5 weight portions, 6 weight portions or 6.5 weight portions or so, and its upper limit can also be 20 weight portions, 19 weight portions, 18 weight portions, 17 weight portions, 16 weight portions, 15 weight portions, 14 weight portions, 13 weight portions, 12 weight portions, 11 weight portions, 10 weight portions, 9 weight portions, 8 weight portions or 7 weight portions or so.Described ratio can also be greater than or equal to any one in the above-mentioned lower limit, be less than or equal to any one in the above-mentioned upper limit, or in the scope of any one in the above-mentioned lower limit to any one in the above-mentioned upper limit.Above ratio can consider the composition of whole resin combination or intended use and change.

[0194] The resin composition may include a catalyst as an additional component. The type of catalyst that may be included is not particularly limited, as long as it can induce appropriate curing according to the type of curing component. For example, when the resin composition is a polyurethane composition and the curable component is a component that forms polyurethane, a polyurethane reaction catalyst may be used as a catalyst.

[0195] The polyurethane reaction catalyst is not particularly limited, and a known component can be used, and as an example, an organic catalyst (such as a tertiary amine) or an organic metal catalyst can be applied. In terms of exerting an appropriate effect by combining with a curing rate modifier to be described below, an organic metal catalyst can be used as a catalyst, for example, a tin catalyst such as an organic tin catalyst can be used.

[0196] When comprising catalyst, ratio can be adjusted according to purpose.For example, relative to the gross weight of 100 weight portions of the reactive compound present in curable component or curable component, the lower limit of the ratio of catalyst can be about 0.001 weight portion, 0.005 weight portion, 0.01 weight portion, 0.05 weight portion, 0.1 weight portion, 0.5 weight portion or 0.55 weight portion, and its upper limit can also be about 10 weight portions, 9 weight portions, 8 weight portions, 7 weight portions, 6 weight portions, 5 weight portions, 4 weight portions, 3 weight portions, 2 weight portions, 1 weight portion or 0.05 weight portion.Described ratio can also be greater than or equal to any one in the above-mentioned lower limit, be less than or equal to any one in the above-mentioned upper limit, or in the scope of any one in the above-mentioned lower limit to any one in the above-mentioned upper limit.Above ratio can consider the composition of whole resin combination or intended use and change.

[0197] Resin combination can include a curing rate modifier to ensure appropriate curing rate. In the present application, the term curing rate modifier means a component that can slow down the curing rate of resin combination compared to the situation where there is no related component. Usually, when the components participating in the curing reaction are mixed under curable conditions, the curing of the resin combination is induced. For example, if the resin combination is a room temperature curing type and is a two-component type comprising a main part and a curing agent part, then when the main part and the curing agent part are mixed at room temperature, the resin combination begins to solidify.

[0198] However, depending on the use of the resin composition, there may be a problem if the curing rate is too fast after the curing is initiated as above.

[0199] Therefore, in the present application, a curing rate modifier can be applied when necessary to ensure a suitable curing rate. In this case, the type of curing rate modifier applied is not particularly limited. For example, a component that can show the effect of controlling the curing rate or showing affinity by competitive reactions with the curable components and catalysts included in the resin combination can be applied.

[0200] When the resin composition is a polyurethane composition, a thiol compound or a carboxylic acid compound may be used as a curing rate regulator. As the curing rate regulator, either a thiol compound or a carboxylic acid compound may be used, or both may be used.

[0201] As the thiol compound, for example, a compound of the following Formula 9 can be used.

[0202] [Formula 9]

[0203] R1-R2-SH

[0204] In Formula 9, R1 may be an alkyl group, an alkoxy group, an aromatic monovalent hydrocarbon group, or -Si(R3)3, and R2 may be a single bond, an alkylene group, or an alkylidene group, wherein the above R3 may be hydrogen, an alkyl group, or an alkoxy group.

[0205] In Formula 9, the case where R2 is a single bond means a structure in which R2 does not exist and a thiol (SH) group is directly connected to R1.

[0206] The alkyl group of R1 or R3 in Formula 9 can 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 can be linear, branched or cyclic. The alkyl group can be optionally substituted with one or more substituents, or can be unsubstituted. When the alkyl group is substituted, the substituent group can be exemplified by a halogen atom, an alkoxy group having 1 to 4 carbon atoms, or a thiol group, etc., but is not limited thereto.

[0207] The alkoxy group of R1 or R3 in Formula 9 can 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 can be linear, branched or cyclic. The alkoxy group can be optionally substituted with one or more substituents, or can be unsubstituted. When the alkoxy group is substituted, the substituent group can be exemplified by 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, but is not limited thereto.

[0208] Here, the aromatic monovalent hydrocarbon group may be exemplified by an aryl group or a heteroaryl group. Here, the aryl group may be exemplified by a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a peryl group, Examples of heteroaryl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, Azolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzo oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, dibenzothiophenyl, benzofuranyl, phenanthroline, thiazolyl, isothiophene Azolyl, The aromatic monovalent hydrocarbon group may be optionally substituted with one or more substituents, or may be unsubstituted. When the aromatic monovalent hydrocarbon group is substituted, the substituent may be exemplified by 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 is not limited thereto.

[0209] In one example, the alkylene group of R2 in Formula 9 can 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, which can be linear or branched. Such an alkylene group can be optionally substituted with one or more substituents, or can be unsubstituted. When the alkylene group is substituted, the substituent group can be exemplified as 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, but is not limited thereto. In addition, in some cases, at least one of the carbon atoms constituting the alkylene group can also be replaced by an oxygen atom.

[0210] In one example, the alkylidene group of R2 in Formula 9 can 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 can be linear or branched. Such an alkylidene group can be optionally substituted with one or more substituents, or can be unsubstituted. When the alkylidene group is substituted, the substituent group can be exemplified as 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, but is not limited thereto. In addition, in some cases, at least one of the carbon atoms constituting the alkylidene group can also be replaced by an oxygen atom.

[0211] As the thiol compound, for example, a monofunctional compound having a hydrocarbon group can be used. The hydrocarbon group can 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, but it can include, for example, 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 of the above formula 9), etc. The case where the thiol compound is a monofunctional compound means that the relevant compound contains one thiol group (-SH).

[0212] The hydrocarbyl of the thiol compound can be an alkyl, alkenyl or alkynyl. At this time, the alkyl can be an alkyl 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 the alkyl can be linear or branched. The alkenyl or alkynyl can be an alkenyl or alkynyl 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 the alkenyl or alkynyl can be linear or branched.

[0213] The thiol compound may be a compound in which one of the hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene or an alkyne is substituted with a thiol group (—SH). In this 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 the 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 the alkene or alkyne may be linear or branched.

[0214] If necessary, the alkane, alkene or alkyne may be optionally substituted with a substituent other than a thiol group, in which case the substituent may be exemplified by an alkoxy group having 1 to 4 carbon atoms and / or a silyl group (e.g., the substituent represented by -Si(R3)3 of the above formula 9), etc., but is not limited thereto.

[0215] The lower limit of the molecular weight (molar mass) of the thiol compound can be about 50 g / mol, 100 g / mol, 150 g / mol, or 200 g / mol, and the upper limit can be about 400 g / mol, 350 g / mol, 300 g / mol, or 250 g / mol. The molecular weight can also be greater than or equal to any one of the above lower limits, less than or equal to any one of the above upper limits, or in the range of any one of the above lower limits to any one of the above upper limits.

[0216] The specific type of such a thiol compound is not particularly limited, and it may be, for example, 1-dodecanethiol or (3-mercaptopropyl)triethoxysilane, or the like.

[0217] When comprising thiol compounds, ratio can be adjusted according to purpose.For example, relative to the gross weight of 100 parts by weight of the reactive compound present in curable component or curable component, the lower limit of the ratio of thiol compounds can be 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 parts by weight or about 1.5 parts by weight, and its upper limit can also be 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 parts by weight, 0.8 parts by weight, 0.7 parts by weight, 0.6 parts by weight, 0.5 parts by weight, 0.4 parts by weight, 0.3 parts by weight or about 0.2 parts by weight.Described ratio can also be greater than or equal to any one in the above-mentioned lower limit, less than or equal to any one in the above-mentioned upper limit, or in the range of any one in the above-mentioned lower limit to any one in the above-mentioned upper limit. The above ratio may be changed in consideration of the composition of the entire resin composition or the intended use.

[0218] When the thiol compound and the catalyst are simultaneously contained in the polyurethane composition, their ratio may be controlled.

[0219] For example, the weight ratio (T / U) of the thiol compound (T) to the urethanization reaction catalyst (U) may have a lower limit of 0.1, 0.5, 1, 1.5, 2, 2.5, or 3, and an upper limit thereof may be about 6, 5.5, 5, 4.5, 4, or 3.5. The ratio (T / U) may also be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range from any of the above lower limits to any of the above upper limits.

[0220] Here, the carboxylic acid compound may be, for example, a monofunctional compound having a hydrocarbon group. The case where the carboxylic acid compound is a monofunctional compound means that the compound includes one carboxyl group (—COOH).

[0221] 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.

[0222] The hydrocarbyl of carboxylic acid compound can be alkyl, alkenyl or alkynyl.At this moment, alkyl can be the alkyl with 1 to 30 carbon atom, 1 to 26 carbon atom, 1 to 22 carbon atom, 1 to 18 carbon atom, 1 to 14 carbon atom, 1 to 10 carbon atom, 1 to 6 carbon atom, 1 to 4 carbon atom, 4 to 30 carbon atom, 5 to 30 carbon atom, 5 to 26 carbon atom, 5 to 22 carbon atom, 5 to 18 carbon atom, 5 to 14 carbon atom or 5 to 10 carbon atom, and this alkyl can be linear or branched.Alkenyl or alkynyl can be the alkenyl or alkynyl with 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 or alkynyl can be linear or branched.

[0223] The carboxylic acid compound may be a compound in which one of the hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene or an alkyne is substituted with a carboxyl group (—COOH). In this 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 the 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 the alkene or alkyne may be linear or branched.

[0224] The lower limit of the molecular weight (molar mass) of carboxylic acid compound can be about 50g / mol, 70g / mol, 90g / mol, 110g / mol, 130g / mol or 140g / mol, and its upper limit can be about 400g / mol, 350g / mol, 300g / mol, 250g / mol, 200g / mol, 150g / mol or 100g / mol.Molecular weight can also be greater than or equal to any one in the above-mentioned lower limit, be less than or equal to any one in the above-mentioned upper limit, or in the scope of any one in the above-mentioned lower limit to any one in the above-mentioned upper limit.

[0225] As carboxylic acid compound, the compound with pKa in the predetermined range can be applied. The lower limit of the pKa of the compound can be about 2, 2.5, 3, 3.5, 4 or 4.5, and the upper limit can be about 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5 or 5. The pKa can also be greater than or equal to any one of the above-mentioned lower limit, less than or equal to any one of the above-mentioned upper limit, or in the range of any one of the above-mentioned lower limit to any one of the above-mentioned upper limit. The above ratio can be changed considering the composition or the intended use of the whole resin combination.

[0226] The specific type of the carboxylic acid compound is not particularly limited, and for example, it may be acetic acid, stearic acid, 2-ethylhexanoic acid, isononanoic acid, or oleic acid, or the like.

[0227] When comprising carboxylic acid compound, ratio can be adjusted according to purpose.For example, relative to the gross weight of 100 weight portions of the reactive compound present in curable component or curable component, the lower limit of the ratio of carboxylic acid compound can be 0.001 weight portion, 0.005 weight portion, 0.01 weight portion, 0.05 weight portion, 0.1 weight portion, 0.5 weight portion or 1 weight portion or so, and its upper limit can also be 10 weight portions, 9 weight portions, 8 weight portions, 7 weight portions, 6 weight portions, 5 weight portions, 4 weight portions, 3 weight portions, 2 weight portions, 1 weight portion, 0.9 weight portion, 0.8 weight portion, 0.7 weight portion, 0.6 weight portion, 0.5 weight portion, 0.4 weight portion, 0.3 weight portion or 0.2 weight portion or so.Described ratio can also be greater than or equal to any one in the above-mentioned lower limit, be less than or equal to any one in the above-mentioned upper limit, or in the scope of any one in the above-mentioned lower limit to any one in the above-mentioned upper limit.Above ratio can consider the composition of whole resin combination or intended use and change.

[0228] When the carboxylic acid compound and the catalyst are simultaneously contained in the polyurethane composition, their ratio may be controlled.

[0229] For example, the weight ratio (C / U) of the carboxylic acid compound (C) to the polyurethane reaction catalyst (U) may have a lower limit of 0.1, 0.5, 1, 1.5, or 2, and an 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 greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range from any of the above lower limits to any of the above upper limits.

[0230] As described above, either or both of the thiol compound and the carboxylic acid compound can be used as a curing rate regulator. In order to ensure a desired viscosity retention zone after curing initiation, to ensure appropriate curing speed and curability after the viscosity retention zone, and to simultaneously control the hardness increase rate, the carboxylic acid compound and the thiol compound can be used simultaneously.

[0231] When a thiol compound and a carboxylic acid compound are simultaneously included 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) can be about 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, or 3, and the upper limit thereof can 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) can also be greater than or equal to any one of the above lower limits, less than or equal to any one of the above upper limits, or within the range of any one of the above lower limits to any one of the above upper limits.

[0232] The resin composition may include the above components and, if necessary, other components. In this case, examples of other components used include viscosity modifiers (e.g., thixotropy imparting agents, diluents, etc.) for increasing or reducing viscosity or for adjusting viscosity according to shear force, dispersants, surface treatment agents, flame retardants, flame retardant aids and / or coupling agents, but are not limited thereto.

[0233] As described above, the resin composition may be a one-component composition or a two-component composition.

[0234] In the case of a two-component composition, the above-mentioned respective components of the resin composition may be independently contained in a main part and a curing agent part which are physically separated.

[0235] In one example, the present application relates to a composition in which the resin composition is composed of a two-component composition (two-component composition).

[0236] Such a two-component composition may at least comprise a main part and a curing agent part, wherein the main part and the curing agent part may be physically separated from each other. When the main part and the curing agent part that are physically separated like this are mixed, a curing reaction may be initiated. When the resin composition is a polyurethane composition, polyurethane may be formed as a result of the curing reaction.

[0237] When building two-component composition, main part can comprise the curable component, catalyst and curing rate regulator in the above-mentioned components at least.In addition, curing agent part can comprise curing agent (polyisocyanate) at least.In such case, main part can not comprise curing agent (polyisocyanate), and curing agent part can not comprise curable component, catalyst and curing rate regulator.

[0238] The filler component may be contained in either the main part and the curing agent part, or may be contained in both the main part and the curing agent part. When the filler component is contained in both the main part and the curing agent part, the same amount of the filler component may be contained in both the main part and the curing agent part.

[0239] For example, in such a case, the upper limit of the ratio of the filler component in the main part can be about 95 wt%, 94.5 wt%, 94 wt%, 93.5 wt%, 93 wt%, 92.5 wt%, 92 wt%, 91.5 wt%, 91 wt%, 90.5 wt%, 90.0 wt%, 89.5 wt%, or 89.0 wt%, and the lower limit can be about 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, about 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, or 88 wt%. The ratio can also be greater than or equal to any one of the above lower limits, less than or equal to any one of the above upper limits, or in the range of any one of the above lower limits to any one of the above upper limits.

[0240] The ratio of the filler component in the main part can be defined as the ratio relative to the curable component of the main part or the total weight of 100 parts by weight of the reactive compound present in the curable component. For example, the lower limit of the ratio of the filler component can 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 can 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 can be greater than or equal to any one of the above lower limits, less than or equal to any one of the above upper limits, or within the range of any one of the above lower limits to any one of the above upper limits.

[0241] Meanwhile, in such a case, the upper limit of the ratio of the filler component in the curing agent part may be about 95 wt%, 94.5 wt%, 94 wt%, 93.5 wt%, 93 wt%, 92.5 wt%, 92 wt%, 91.5 wt%, 91 wt%, 90.5 wt%, 90.0 wt%, 89.5 wt%, or 89.0 wt%, and the lower limit thereof may be about 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, about 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, or 88 wt%. The ratio may also be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range from any of the above lower limits to any of the above upper limits.

[0242] The ratio of the filler component in the curing agent part can also be defined as the ratio of the curing agent (polyisocyanate) relative to 100 parts by weight in the curing agent part. For example, the lower limit of the ratio of the filler component can 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 its upper limit can 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 can also be greater than or equal to any one of the above lower limits, less than or equal to any one of the above upper limits, or in the range of any one of the above lower limits to any one of the above upper limits.

[0243] A catalyst, a plasticizer, a flame retardant, etc. may be contained in the main part and / or the curing agent part as other components as necessary.

[0244] In the two-component composition, the volume ratio (P / N) of the volume of the main part (P) to the volume of the curing agent part (N) may have a lower limit of about 0.8, 0.85, 0.9, 0.95, or 1, and an upper limit thereof may be 1.2, 1.15, 1.1, 1.05, or 1. The ratio (P / N) may also be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range from any of the above lower limits to any of the above upper limits.

[0245] In one example, the two-component composition may be formulated so that when the main part and the curing agent part have the above volume ratio, the above-mentioned equivalent ratio (OH / NCO) may be ensured.

[0246] Such a two-component composition or its cured body may also exhibit adhesion to aluminum and polyester, thermal conductivity, hardness, radius of curvature, insulation, flame retardancy, specific gravity, shrinkage, coefficient of thermal expansion and / or 5% weight loss temperature in thermogravimetric analysis (TGA), etc.

[0247] The resin composition (single component composition or two component composition) can show a suitable curing rate after curing initiation. Here, curing initiation occurs when the curable component and curing agent contained in the resin composition contact under conditions that can induce curing. Therefore, in the case of a single component composition, curing can be initiated when the relevant composition is placed under curing initiation conditions, and in the case of a two component composition, curing can be initiated when the main part and the curing agent part are mixed under curing initiation conditions.

[0248] For example, when the resin composition is a curable composition, the curable composition may exhibit a curing rate such that V1 according to the following Equation 1 is within a predetermined range.

[0249] [Equation 1]

[0250] V1=V 初始 / t

[0251] In Equation 1, V 初始 is the initial viscosity of the curable composition at the curing initiation point (unit: cps), and t is the time required for the viscosity of the curable composition to double compared to the initial viscosity at the curing initiation point (unit: minute).

[0252] As described above, curing occurs when the components that participate in the curing reaction are brought into contact under conditions that allow curing.

[0253] For example, when the curable composition is a main part comprising a curable component, a curing rate regulator, a polyurethane reaction catalyst, and a filler component, the curing initiation point is the time point when the main part (curable composition) and the curing agent component (e.g., the curing agent component or the curing agent part comprising a polyisocyanate) are mixed under conditions capable of curing. The mixing for determining the above equation 1 can be performed so that the main part and the curing agent component satisfy the above volume ratio (P / N) and / or equivalent ratio (OH / NCO).

[0254] Therefore, in such a case, the initial viscosity may be the initial viscosity of the mixture of the main part and the curing agent component.

[0255] The method of determining V1 in Equation 1 above is summarized in the Examples.

[0256] The lower limit of V1 in the above equation 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 20,000 cps / min, 18,000 cps / min, 16,000 cps / min, 14,000 cps / min, 12,000 cps / min, or 15,000 cps / min. V1 may be about 10,000 cps / minute, 10,000 cps / minute, 9,500 cps / minute, 9,000 cps / minute, 8,500 cps / minute, 8,000 cps / minute, 7,500 cps / minute, 7,000 cps / minute, 6,500 cps / minute, 6,000 cps / minute, 5,500 cps / minute, 5,000 cps / minute, 4,500 cps / minute, 4,000 cps / minute, 3,500 cps / minute, 3,000 cps / minute, or about 2,500 cps / minute. V1 may also be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range from any of the above lower limits to any of the above upper limits.

[0257] In the above equation 1, V 初始 The upper limit 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 may be about 10,000 cps, 50,000 cps, 100,000 cps, 150,000 cps, or 200,000 cps. 初始 It may also be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or within the range from any of the above lower limits to any of the above upper limits.

[0258] The curable composition may exhibit a predetermined Shore OO hardness detection time after the cure initiation point. Here, the Shore OO hardness detection time means the time taken for the Shore OO hardness to be first detected during the periodic measurement of the hardness of the curable composition after the cure initiation point. That is, when the curable composition is placed under cure initiation conditions, the hardness increases as the cure proceeds, so that if the Shore OO hardness detection time is short, this means that the cure rate is fast.

[0259] Here, the curing initiation point or the curable composition for which the hardness is measured means as described in Equation 1 above.

[0260] Therefore, for example, when the curable composition is a main part comprising a curable component, a curing rate regulator, a polyurethane reaction catalyst and a filler component, the curing initiation point is a time point when the main part (curable composition) and the curing agent component (e.g., the curing agent component or the curing agent part comprising a polyisocyanate) are mixed under conditions capable of curing, and the mixing for determining the above equation 1 can be performed so that the main part and the curing agent component satisfy the above volume ratio (P / N) and / or equivalent ratio (OH / NCO).

[0261] In such a case, the hardness may be measured on a mixture of the main part and the curing agent component.

[0262] The lower limit of the Shore OO hardness test time can 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 its upper limit can 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 test time can also be greater than or equal to any one of the above-mentioned lower limit, less than or equal to any one of the above-mentioned upper limit, or in the range of any one of the above-mentioned lower limit to any one of the above-mentioned upper limit.

[0263] The present application also relates to a thermal interface material (TIM). The thermal interface material may be a cured product of a resin composition.

[0264] Therefore, the thermal interface material may also exhibit adhesion to aluminum and polyester, thermal conductivity, hardness, radius of curvature, insulation properties, flame retardancy, specific gravity, shrinkage, coefficient of thermal expansion and / or 5% weight loss temperature in thermogravimetric analysis (TGA), etc. as described above.

[0265] Therefore, the thermal interface material may include the components included in the resin composition, or components derived from the components.

[0266] For example, if the resin composition is a polyurethane composition, the thermal interface material may include polyurethane.

[0267] Polyurethane can be formed by the reaction of the above-mentioned reactive compounds with a curing agent (polyisocyanate).

[0268] Thus, the polyurethane may comprise units derived from reactive compounds.

[0269] For example, if the reactive compound comprises a polyester backbone (eg, polycaprolactone backbone) or a polyether backbone (eg, polyalkylene backbone) as described above, the polyurethane may comprise polyester units (eg, polycaprolactone units) or polyether units (eg, polyalkylene units).

[0270] For example, the polyurethane may include units of Formula 2, Formula 3, Formula 5 and / or Formula 6 as described above.

[0271] Furthermore, the polyurethane may contain a hydrocarbon group derived from the above-mentioned oil-modified compound, ie, a linear or branched hydrocarbon group having 3 or more carbon atoms.

[0272] As described above, the lower limit of the number of carbon atoms in the linear or branched hydrocarbon group can be about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or 17, and the upper limit thereof can also 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 can be less than or equal to any of the above upper limits, greater than or equal to any of the above lower limits, or in the range of any of the above lower limits to any of the above upper limits.

[0273] The linear or branched hydrocarbon group may or may not contain double bonds. In the case of containing double bonds, such double bonds may be conjugated double bonds or cis double bonds.

[0274] The specific type of alkyl can be exemplified as alkyl, alkenyl or alkynyl. In one example, alkyl can be connected to polyurethane backbone via carbonyl or carbonyloxy, in which case alkyl can be alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy or alkynylcarbonyloxy. Here, the carbon number in alkyl, alkenyl or alkynyl can also be greater than or equal to any one of the lower limits of the carbon number of linear or branched alkyl as described above, less than or equal to any one of the upper limits of the carbon number of linear or branched alkyl as described above, or in the range of any one of the lower limits of the carbon number of linear or branched alkyl as described above to any one of the upper limits of the carbon number of linear or branched alkyl as described above.

[0275] The alkyl, alkenyl or alkynyl group may be linear or branched, and may be optionally substituted with one or more substituents. When a substituent is present, the type of the substituent is not particularly limited, and for example, a halogen atom (eg, fluorine) may be exemplified as a substituent.

[0276] As described above, the hydrocarbon group may be included in the structures of Formulae 1 to 6 described above.

[0277] Furthermore, the polyurethane may include units derived from the above-mentioned curable component, so that it may include units of the first reactive compound and units of the second reactive compound, and as units of the second reactive compound, may include units of the third reactive compound and units of the fourth reactive compound.

[0278] The specific descriptions of the reactive compounds and the ratios therebetween can be applied in the same manner as those described in the resin composition.

[0279] In addition, the polyurethane may include units derived from the above-mentioned curing agent, so that it may include the above-mentioned polyisocyanate units, for example, polyisocyanate units with trifunctionality or more and polyisocyanate units with difunctionality. The specific description of the polyisocyanate and the ratio between them may be applied in the same manner as those described in the resin composition.

[0280] The polyurethane contained in the thermal interface material may contain at least one hydroxyl group. That is, the polyurethane may be synthesized by reacting the hydroxyl group of the reactive compound with the isocyanate group of the polyisocyanate as a curing agent to form a urethane bond, wherein at least one hydroxyl group may be retained in the final polyurethane by adjusting the hydroxyl equivalent of the reactive compound to be larger in the process. For example, the polyurethane may contain hydroxyl groups in the following amounts: 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, 0.1 mol / g to 0.5 mol / g or so. By allowing hydroxyl groups to remain in polyurethane at such a ratio, a thermal interface material having desired properties can be more effectively formed. The method of allowing hydroxyl groups to remain in polyurethane as above is not particularly limited, and the polyurethane can be formed by adjusting the equivalent ratio of OH / NCO during the reaction process.

[0281] The thermal interface material may include polyurethane and components of the resin composition as described above, such as a curing rate regulator, a plasticizer, a catalyst and / or a filler component, and the specific description of the components and their weight ratios may apply in the same manner as in the above resin composition.

[0282] The present application also relates to a product comprising a resin composition or a cured product thereof (thermal interface material or heat transfer material). The resin composition of the present application or a cured product thereof can be effectively used as a heat dissipation material. Therefore, the product may include a heat generating component. The term heat generating component means a component that emits heat during use, and the type is not particularly limited. Representative heat generating components include various electrical / electronic products, including battery cells, battery modules or battery packs, etc.

[0283] The product of the present application may include, for example, a heat-generating component and a resin composition (or a two-component composition) or a cured product thereof adjacent to the heat-generating component.

[0284] The specific method for configuring the product of the present application is not particularly limited. If the resin composition or two-component composition of the present application or its cured product is used as a heat dissipation material, the product can be configured in various known ways.

[0285] Beneficial Effects

[0286] The present application provides a curable composition, a thermal interface material (TIM) and its use. In the present application, the curable composition or the thermal interface material, etc. can show low adhesion to a given adherend while showing high thermal conductivity. In addition, in the present application, low adhesion can be achieved without using adhesion regulating components such as plasticizers or in a state where the use ratio thereof is minimized.

[0287] In the present application, the curable composition may also exhibit a precisely controlled curing rate and simultaneously have excellent curability.

[0288] The present application may also provide a product comprising the curable composition or a cured product thereof or a thermal interface material. BRIEF DESCRIPTION OF THE DRAWINGS

[0289] Figure 1 is a diagram of a device for measuring load values.

[0290] Figure 2 and Figure 3 The analysis results of the reactive compounds synthesized in Preparation Example 1 and Preparation Example 2 are shown respectively.

[0291] Figure 4 and Figure 5 They are graphs recording the changes in viscosity and hardness over time, respectively. DETAILED DESCRIPTION

[0292] Hereinafter, the present application will be specifically described through examples, but the scope of the present application is not limited by the following examples.

[0293] The cured body mentioned below is formed by mixing the main part of the resin composition prepared as a two-component type in the examples and the curing agent part so as to satisfy the OH / NCO equivalent ratio described in each example, and then keeping the mixture at room temperature (25° C.) for about 24 hours.

[0294] In this example, physical properties were evaluated in the following manner.

[0295] 1. Thermal conductivity

[0296] The thermal conductivity of the resin composition (curable composition) or its cured body is measured by the hot plate method according to ISO 22007-2 standard. Specifically, the mixture in which the main part and the curing agent part are mixed in a volume ratio of 1:1 in the embodiment or comparative example is placed in a mold with a thickness of about 7 mm, cured, and the thermal conductivity is measured in the through plane direction using a hot plate device. As specified in the above standard (ISO 22007-2), the hot plate device is a device that can check the thermal conductivity by measuring the temperature change (resistance change) when heating a sensor having a nickel wire double helix structure, and the thermal conductivity is measured according to this standard.

[0297] 2. Measurement of Adhesion to Polyester

[0298] Adhesion to polyester is evaluated for a sample prepared by attaching a PET (polyethylene terephthalate) film to an aluminum plate. A film having a width of about 10 mm and a length of about 200 mm is used as the PET film, and an aluminum plate having a width and a length of 100 mm is used as the aluminum plate. The resin composition is applied to the entire surface of the aluminum plate and kept at room temperature (about 25 ° C) for about 24 hours in a state where the PET film is attached to the resin composition to prepare the sample. At this time, the entire width of the PET film and a length portion of about 100 mm are attached to the aluminum plate via the resin composition. In a state where the aluminum plate of the sample is fixed, the adhesion is measured when the PET film is peeled off from the aluminum plate in the longitudinal direction. Attachment is performed by applying a resin composition (a mixture of a main part and a curing agent part having a volume ratio of 1:1) to the aluminum plate to have a thickness of about 2 mm after curing, and then the PET film is closely attached to the layer of the resin composition, and they are kept at room temperature (about 25 ° C) for about 24 hours to cure the resin composition. The peeling was performed at a peeling rate of about 0.5 mm / min and a peeling angle of 180 degrees until the PET film was completely peeled off.

[0299] 3. Measurement of adhesion to aluminum

[0300] Uncured resin combination (mixture of the main part and curing agent part of 1:1 in volume ratio) is coated on the center of the aluminum substrate of horizontal length and vertical length being respectively 2cm and 7cm with a width of 2cm and a length of about 2cm, and the aluminum substrate of horizontal length and vertical length being respectively 2cm and 7cm is attached to coating again, and resin combination is solidified by keeping this state.Herein, two aluminum substrates are attached to form an angle of 90 degrees to each other.Hereinafter, when upper aluminum substrate is fixed, lower aluminum substrate is pressed at a speed of 0.5mm / min to measure the force when lower aluminum substrate is separated, and the adhesive force to aluminum is obtained by dividing the maximum force measured in the process by the area of ​​sample.

[0301] 4. Hardness measurement

[0302] The hardness of the cured body of the resin composition is measured according to ASTM D 2240 and JIS K 6253. It is performed using an ASKER durometer hardness device, wherein the initial hardness is measured by applying a load of 1 Kg or more (about 1.5 Kg) to the surface of the sample (cured body) in a flat state, and after 15 seconds, the hardness is evaluated by determining a stable measured value.

[0303] 5. Viscosity measurement

[0304] The viscosity was measured using a Brookfield HB DB3T device at 0.01 s. -1 Up to 10.0 seconds -1 The viscosity is measured at room temperature (about 25°C) under the condition of a shear rate of 2.4 seconds. Unless otherwise specified, the viscosity mentioned in this specification is the shear rate of 2.4 seconds. -1 The viscosity at the point.

[0305] 6. Measurement of curing rate (hardness determination time)

[0306] The curing rate of the resin composition is evaluated by the change of hardness over time. At this time, the hardness is measured according to ASTM D 2240 and JIS K 6253 standards in the same manner as described above. The main part and the curing agent part are mixed in a volume ratio of 1: 1, and the hardness is confirmed every 30 minutes while the mixture is kept at room temperature (about 25°C), and the curing rate is evaluated by determining the time when the Shore OO hardness is first confirmed.

[0307] 7. Measurement of curing rate (viscosity increase time)

[0308] The curing rate of the resin composition was also evaluated by the change in viscosity over time.

[0309] Specifically, the curing rate was evaluated by determining V1 in the following Equation 1.

[0310] [Equation 1]

[0311] V1=V 初始 / t

[0312] In Equation 1, V 初始 is the initial viscosity of the mixture in which the curable composition is mixed with the curing agent component having the polyisocyanate (unit: cps), and t is the time required for the viscosity of the mixture to double compared with the initial viscosity (unit: minute).

[0313] Specifically, V 初始 is a value obtained by loading a mixture in which the main part and the curing agent part prepared in each Example or Comparative Example were mixed at a volume ratio of 1:1 into a viscosity measuring device (Brookfield HB DB3T type device), holding it for 2.4 seconds. -1 The viscosity was stabilized by keeping the viscosity at a shear rate of 1.50 μm for about 60 seconds and then measuring the viscosity.

[0314] After loading it into the Brookfield HB DB3T viscometer and holding for 2.4 seconds -1 The viscosity is measured over time when the shear rate is controlled.

[0315] 8. Measurement of curvature radius

[0316] The curvature radius of the solidified body was evaluated using solidified bodies having a width, length and thickness of 1 cm, 10 cm and 2 mm, respectively. When the solidified body was attached to a cylinder having various radii and bent in the longitudinal direction, the curvature radius was the minimum radius of the cylinder at which no cracks occurred in the solidified body.

[0317] 9. Measurement of average particle size

[0318] The average particle size of the filler is the D50 particle size of the filler, which is the particle size measured by Marvern's MASTERSIZER3000 device according to the ISO-13320 standard. When measuring, ethanol is used as a solvent. The incident laser is scattered by the filler dispersed in the solvent, and the intensity value and directionality of the scattered laser light change according to the size of the filler. The Mie theory is used for analysis, and the D50 particle size can be obtained. Through the above analysis, the distribution can be obtained by converting to the diameter of a sphere with the same volume as the dispersed filler, and the particle size can be evaluated by obtaining the D50 value as the median of the distribution.

[0319] 10.Module processability assessment

[0320] The resin composition (a mixture of the main part and the curing agent part in a volume ratio of 1:1) was applied to a square-shaped aluminum plate with a width and length of 8 cm and a thickness of about 2 mm, and kept for about 24 hours under room temperature (about 25°C) and normal humidity (about 40% relative humidity) conditions for curing. Subsequently, when the cured product was peeled off from the aluminum plate, the module processability was evaluated according to the following criteria.

[0321] <Evaluation Criteria>

[0322] O: When the cured product of the resin composition peels off in a flake form without leaving any residue on the aluminum plate

[0323] X: When the cured product of the resin composition cannot be peeled off from the aluminum plate, or even if peeled off, a residue remains

[0324] 11. Clear waiting time assessment

[0325] The purging waiting time is estimated by measuring the load value.

[0326] Load value (unit: kgf) is used as follows Figure 1 The disclosed device was evaluated. Figure 1 The device is a device 1 in which two barrels 2, 2a, 2b and a static mixer 5 are connected. In the device 1, as barrels 2, 2a, 2b, barrels (Sulzer, AB050-01-10-01) having a circular material injection part with a diameter of 18 mm, a circular material discharge part 4, 4a, 4b with a diameter of 3 mm, a height of 100 mm and an internal volume of 25 ml are used. As the static mixer 5, a stepped static mixer (Sulzer, MBH-06-16T) having a circular discharge part 7 with a diameter of 2 mm and 16 elements is used. As the pressurizing device 3, 3a, 3b of the device (a device for pushing the composition loaded on the barrel), a TA (texture analyzer) is used.

[0327] In order to measure the load value, the main part is loaded into either of the two barrels 2a, 2b, and the curing agent part is loaded into the other barrel. Subsequently, the main part and the curing agent part are injected into the static mixer 5 by pressurizing them at a constant speed of 1 mm / sec with the pressurizing device 3, 3a, 3b, and mixed in the mixer 5, so that they are discharged from the discharge portion 7. In the above process, the force applied to the pressurizing device is measured from the time when pressurization is started with the pressurizing device to the discharge time. In the above process, the maximum value of the force applied to the pressurizing device is designated as the load value.

[0328] After measuring the load value, the pressure application is stopped, and the device 1 is maintained at room temperature (about 25 °C). In this case, the mixture of the main part and the curing agent part is kept in the mixer 5. After waiting for a certain period of time, the pressure application is started again using the pressure application device, and the load value is measured in the same manner as above. In this process, the waiting time when the load value reaches 60 kgf is designated as the purge waiting time.

[0329] 12. Measurement of weight-average molecular weight

[0330] The weight-average molecular weight (Mw) is measured using GPC (gel permeation chromatography). Specifically, the weight-average molecular weight (Mw) can be measured as follows: The sample to be analyzed is added to a 5 mL vial, diluted to a concentration of about 1 mg / mL with a THF (tetrahydrofuran) solvent, and then the standard sample for calibration and the analysis sample are filtered through a syringe filter (pore size: 0.45 μm). Using the ChemStation of Agilent technologies as the analysis program, the weight-average molecular weight (Mw) can be obtained by comparing the elution time of the sample with the calibration curve.

[0331] <GPC measurement conditions>

[0332] Instrument: 1200 series of Agilent technologies

[0333] Column: TL Mix.A&B of Agilent technologies is used

[0334] Solvent: THF (tetrahydrofuran)

[0335] Column temperature: 35 °C

[0336] Sample concentration: 1 mg / mL, 200 μl injection

[0337] Standard sample: Polystyrene (MP: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485) is used

[0338] 13. GC-MS (gas chromatography - mass spectrometry) analysis

[0339] An Agilent instrument was used as a measuring instrument for GC-MS analysis (GC (gas chromatography) instrument: model 7890, MS (mass spectrometry) detector: model 5977B). The sample (cured product of the resin composition) was dissolved in a solvent (chloroform) at a concentration of 100 mg / mL, and the supernatant was extracted and filtered through a 0.2 μm syringe filter, and then loaded into the GS-MS analysis instrument. Analysis was performed under the following conditions, and quantitative analysis was performed by detecting the intensities of the peaks of the target substances (1-dodecanethiol and 2-ethylhexanoic acid).

[0340] <GC measurement conditions>

[0341] Column: HP-5MS from Agilent technologies

[0342] Gas flow rate: Column (He): 1 mL / min

[0343] Ionization mode: EI

[0344] Syringe temperature: 300 °C

[0345] Injection volume: 0.5 μl

[0346] Preparation Example 1.

[0347] The oil-modified compound (reactive compound) of the following formula A was prepared in the following manner.

[0348] [Formula A]

[0349]

[0350] In formula A, n and m are each greater than 0, and the sum (n + m) is about 4.8.

[0351] Polycaprolactone polyol (Capa 3031, Perstorp) and isononanoic acid as a saturated fatty acid were mixed at a weight ratio of 1:0.53 (Capa 3031: isononanoic acid). Subsequently, a catalyst (tin(II) 2-ethylhexanoate (Sigma-Aldrich)) was added in an amount of 0.1 part by weight relative to 100 parts by weight of the mixture, and the mixture was stirred at 150 °C for 30 minutes under an inert gas purge condition and maintained simultaneously. Subsequently, a small amount of xylene was added as an azeotropic solution, the temperature was raised to 200 °C, the reaction was carried out for 3 hours or longer, and then the pressure was reduced to 80 Torr or less, and xylene and unreacted products were removed. The reaction product was cooled and then filtered to obtain the target product (compound of formula A).

[0352] As a result of GPC analysis of the target product, the weight average molecular weight was about 710 g / mol. Figure 2It is a figure which shows the result of GPC analysis of a target product.

[0353] Preparation Example 2.

[0354] The oil-modified compound (reactive compound) of the following formula B was prepared in the following manner.

[0355] [Formula B]

[0356]

[0357] In Formula B, p and q are each greater than 0, and the sum (p+q) is about 4.8.

[0358] Polycaprolactone polyol (Capa 3031, Perstorp) and isononanoic acid as saturated fatty acid are mixed in a weight ratio of 1:1.06 (Capa 3031: isononanoic acid). Subsequently, relative to the mixture of 100 parts by weight, a catalyst (tin (II) of 2-ethylhexanoate) (Sigma-Aldrich) is added in an amount of 0.1 parts by weight, and the mixture is stirred at 150 ° C for 30 minutes under an inert gas purge condition, and maintained simultaneously. Subsequently, a small amount of xylene is added as an azeotropic solution, the temperature is raised to 200 ° C, the reaction is carried out for 3 hours or more, and then the pressure is reduced to 80 torr or less, removing xylene and unreacted product. The reaction product is cooled and then filtered to obtain the target product (compound of formula B).

[0359] As a result of GPC analysis performed on the target product, the weight average molecular weight was about 814 g / mol. Figure 3 It is a figure which shows the result of GPC analysis of a target product.

[0360] Example 1.

[0361] Preparation of the main part

[0362] The oil-modified compound of Preparation Example 1 and Preparation Example 2, the non-oil-modified compound (Kuraray, F-2010), the polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), the thiol compound (1-dodecyl mercaptan), the carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), the filler component and the plasticizer (diisononyl adipate) were mixed in a weight ratio of 4.59:5.1:0.51:0.066:0.2:0.066:88.8:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer) to prepare the main part. The filler component was prepared by mixing a first alumina filler having an average particle size of about 70 μm, a second alumina filler having an average particle size of about 20 μm, and a third alumina filler having an average particle size of about 1 μm. The volume ratio after mixing is about 6:2:2 (first alumina filler: second alumina filler: third alumina filler).

[0363] Preparation of curing agent

[0364] Polyisocyanate (Tolonate HDT-LV2, manufactured by Vencorex) was used as a curing agent. The main part was prepared by mixing the polyisocyanate, the filler component and the plasticizer (diisononyl adipate) in a weight ratio of 5.08:4.78:90.1 (polyisocyanate: filler: plasticizer). The filler component was prepared by mixing a first alumina filler having an average particle size of about 70 μm, a second alumina filler having an average particle size of about 20 μm, and a third alumina filler having an average particle size of about 1 μm. The volume ratio after mixing was about 6:2:2 (first alumina filler: second alumina filler: third alumina filler).

[0365] When the curing agent part and the main part are formulated in a volume ratio of 1:1, the curing agent part is prepared so that the equivalent ratio (OH / NCO) of the hydroxyl group (OH) present in the main part to the isocyanate group (NCO) present in the curing agent part is about 100.

[0366] Preparation of resin composition and cured product

[0367] The resin composition (curable composition) was prepared by separately preparing a main part and a curing agent part, mixing the main part and the curing agent part at a volume ratio of about 1:1, and then maintaining at room temperature (about 25° C.) to form a cured body.

[0368] Example 2.

[0369] The main part was prepared in the same manner as in Example 1, except that the formulation weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), thiol compound (1-dodecyl mercaptan), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.59:5.1:0.51:0.048:0.096:0.096:88.9:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0370] Example 3.

[0371] The main part was prepared in the same manner as in Example 1, except that the formulation weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), thiol compound (1-dodecyl mercaptan), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.59:5.1:0.51:0.06:0.11:0.11:88.8:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0372] Example 4.

[0373] The main part was prepared by mixing the oil-modified compounds of Preparation Example 1 and Preparation Example 2, the non-oil-modified compound (Kuraray, F-2010), the polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), the thiol compound (1-dodecyl mercaptan), the carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), the filler component and the plasticizer (diisononyl adipate) in a weight ratio of 4.59:5.1:0.51:0.03:0.055:0.055:89:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer). As the filler component, the same component as in Example 1 was used.

[0374] In the same manner as in Example 1, a curing agent part, a resin composition and a cured body were prepared.

[0375] Example 5.

[0376] The main part was prepared by mixing the oil-modified compounds of Preparation Example 1 and Preparation Example 2, the non-oil-modified compound (Kuraray, F-2010), the polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), the thiol compound (1-dodecyl mercaptan), the carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), the filler component and the plasticizer (diisononyl adipate) in a weight ratio of 4.59:5.1:0.51:0.018:0.033:0.033:89:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer). As the filler component, the same component as in Example 1 was used.

[0377] In the same manner as in Example 1, a curing agent part, a resin composition and a cured body were prepared.

[0378] Example 6.

[0379] The main part was prepared by mixing the oil-modified compound of Preparation Example 1 and Preparation Example 2, the non-oil-modified compound (Kuraray, F-2010), the polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), the thiol compound (1-dodecyl mercaptan), the carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), the filler component and the plasticizer (diisononyl adipate) in a weight ratio of 4.59:5.11:0.51:0.012:0.022:0.022:89:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer). As the filler component, the same component as in Example 1 was used.

[0380] In the same manner as in Example 1, a curing agent part, a resin composition and a cured body were prepared.

[0381] Example 7.

[0382] The main part was prepared by mixing the oil-modified compounds of Preparation Example 1 and Preparation Example 2, the non-oil-modified compound (Kuraray, F-2010), the polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), the thiol compound (1-dodecyl mercaptan), the carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), the filler component and the plasticizer (diisononyl adipate) in a weight ratio of 4.6:5.11:0.51:0.0066:0.011:0.011:89:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: 2-EHA: filler: plasticizer). As the filler component, the same component as in Example 1 was used.

[0383] In the same manner as in Example 1, a curing agent part, a resin composition and a cured body were prepared.

[0384] Comparative Example 1.

[0385] A main part, a curing agent part, a resin composition and a cured body were prepared in the same manner as in Example 1, except that the thiol compound and the carboxylic acid compound were not used in the preparation of the main part.

[0386] Comparative Example 2.

[0387] The main part was prepared in the same manner as in Example 1, except that the formulation weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.59:5.10:0.51:0.066:0.13:88.9:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0388] Comparative Example 3.

[0389] The main part was prepared in the same manner as in Example 1, except that the formulation weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), thiol compound (1-dodecyl mercaptan), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.59:5.1:0.51:0.066:0.13:88.9:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0390] Comparative Example 4.

[0391] The main part was prepared in the same manner as in Example 1, except that the formulation weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), thiol compound (1-dodecyl mercaptan), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.59:5.1:0.51:0.066:0.153:88.9:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0392] Comparative Example 5.

[0393] The main part was prepared in the same manner as in Example 1, except that the formulation weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), thiol compound (1-dodecyl mercaptan), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.59:5.1:0.51:0.066:0.2:88.8:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0394] Comparative Example 6.

[0395] The main part was prepared in the same manner as in Example 1, except that the weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.6:5.11:0.51:0.048:89:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0396] Comparative Example 7.

[0397] The main part was prepared in the same manner as in Example 1, except that the formulation weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), thiol compound (1-dodecyl mercaptan), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.59:5.1:0.51:0.048:0.096:89:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0398] Comparative Example 8.

[0399] The main part was prepared in the same manner as in Example 1, except that the formulation weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.59:5.1:0.51:0.048:0.096:89:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0400] Comparative Example 9.

[0401] The main part was prepared in the same manner as in Example 1, except that the formulation weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), thiol compound (1-dodecyl mercaptan), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.59:5.1:0.51:0.06:0.11:88.9:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: thiol: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0402] Comparative Example 10.

[0403] The main part was prepared in the same manner as in Example 1, except that the formulation weight ratio of the oil-modified compound, non-oil-modified compound (Kuraray, F-2010), polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), filler component and plasticizer (diisononyl adipate) of Preparation Example 1 and Preparation Example 2 was changed to 4.59:5.10:0.51:0.060:0.11:88.9:0.71 (Preparation Example 1: Preparation Example 2: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent part, resin composition and cured body were prepared in the same manner as in Example 1.

[0404] The results of the physical property evaluations summarized for the above embodiments and comparative examples are shown in Tables 1 to 4 below. In Tables 1 and 2 below, the hardness (Shore OO hardness and Shore A hardness) is the hardness measured after a mixture of the main part and the curing agent part in a volume ratio of 1:1 is kept at room temperature (about 25°C) for 24 hours.

[0405] In the following Tables 1 to 4, the curing rate (hardness) is the time (unit: hour) until the Shore OO hardness is first determined when the hardness is determined every 30 minutes when the main part and the curing agent part in each Example or Comparative Example are mixed in a volume ratio of 1:1 and the mixture is maintained at room temperature (about 25° C.) (related to Measurement 6. Measurement of the curing rate (hardness determination time)).

[0406] In the following Tables 1 to 4, the curing rate (viscosity) is t (unit: minute) of Equation 1 in the method for measuring the curing rate (viscosity increase time), and V 初始 and V1 are V in equation 1 above. 初始 and V1.

[0407] [Table 1]

[0408]

[0409] [Table 2]

[0410]

[0411] [Table 3]

[0412]

[0413] [Table 4]

[0414]

[0415] Test example 1.

[0416] In order to determine the curing slowing effect by the action of the thiol compound and the carboxylic acid compound, the resin compositions of Example 1 and Comparative Examples 1, 2 and 5 were evaluated. The main part and the curing agent part in each resin composition of the above Example or Comparative Example were mixed at a volume ratio of 1:1, and the changes in viscosity and hardness over time were evaluated. The results are shown in Figure 4 and Figure 5 middle.

[0417] Observing the graph, in the case of Example 1 containing both a thiol compound and a carboxylic acid compound, a viscosity retention section in which the viscosity is maintained after mixing is determined, and the viscosity increases rapidly after the viscosity retention section, whereby it can be determined that curability is stably secured after curing is slowed down. In addition, in terms of hardness, it can be determined that there is a section in which hardness cannot be measured for an appropriate amount of time.

[0418] It can be known that immediately after the main part of Comparative Example 1 not containing a thiol compound and a carboxylic acid compound and the curing agent part were mixed, the viscosity increased rapidly, and the hardness also began to be determined and increased at a rapid point in time immediately after the mixing.

[0419] Compared with Comparative Example 1, in the case of Comparative Example 2 containing only a carboxylic acid compound, the increasing trend of the viscosity was determined to be slow, but there was no viscosity retention section in which the viscosity was kept constant at the start of mixing, the hardness was determined too late, and the viscosity did not increase well over time, from which it can be known that the curability was also insufficient.

[0420] In the case of Comparative Example 5 containing only a thiol compound, a viscosity maintaining section was observed, but it can be known that the viscosity maintaining section is relatively short, and the viscosity increase rate after the viscosity maintaining section is too fast. In addition, in the case of Comparative Example 5, the hardness also increases too fast, and thus it can be expected that it will not be easy to ensure working time during large-area application, etc.

[0421] Test example 2.

[0422] In the following Table 5, the contents of the thiol compound and the carboxylic acid compound in the main parts and the cured products of Examples 2 to 7 are summarized.

[0423] In the following Table 5, the formulated amounts are the amounts of the thiol compound and the carboxylic acid compound added during production (unit: weight %), and the detected amounts are the amounts detected by GC-MS (gas chromatography-mass spectrometry) analysis (unit: weight %).

[0424] It can be known from the results of Table 5 that the thiol compound and the carboxylic acid compound added to the main part remain in the cured body after the curing reaction. In Examples 5 to 8, there are cases where the thiol compound and / or the carboxylic acid compound are not detected, but this result is caused by a small addition amount, and considering the results of Examples 2 to 4, it can be inferred that the carboxylic acid compound and the thiol compound are present in the cured bodies of Examples 5 to 8.

[0425] [Table 5]

[0426]

Claims

1. A thermal interface material, comprising: Polyurethane; one or more compounds selected from the group consisting of thiol compounds and carboxylic acid compounds; and Filling component. 2 . The thermal interface material according to claim 1 , having a thermal conductivity of 2.0 W / mK or greater.

3. The thermal interface material according to claim 1, wherein the adhesion of the thermal interface material to aluminum is 0.15 N / mm 2 or smaller.

4. The thermal interface material according to claim 1, wherein the adhesion of the thermal interface material to polyester is 100 gf / cm or less. 5 . The thermal interface material according to claim 1 , having a Shore OO hardness of 95 or less. The thermal interface material according to claim 1 , wherein the curvature radius of the thermal interface material is 20 or less. 7 . The thermal interface material of claim 1 , wherein the polyurethane comprises a hydroxyl group in an amount of 0.1 mol / g or more.

8. The thermal interface material of claim 1, wherein the polyurethane comprises polycaprolactone polyol units.

9. The thermal interface material of claim 1, wherein the polyurethane comprises a branched hydrocarbon chain, and wherein the branched hydrocarbon chain has 5 or more carbon atoms.

10. The thermal interface material of claim 1, wherein the polyurethane comprises units of a first reactive compound having one hydroxyl group and units of a second reactive compound having two or more hydroxyl groups. 11 . The thermal interface material of claim 10 , wherein the units of the second reactive compound include units of a third reactive compound having two hydroxyl groups and units of a fourth reactive compound having three or more hydroxyl groups. 12 . The thermal interface material of claim 1 , wherein the polyurethane comprises a polyisocyanate unit having a trifunctionality or more and a polyisocyanate unit having a difunctionality. 13 . The thermal interface material according to claim 1 , wherein the thiol compound is a monofunctional compound having a hydrocarbon group. 14 . The thermal interface material of claim 13 , wherein the molecular weight of the monofunctional compound is in the range of 50 g / mol to 400 g / mol.

15. The thermal interface material according to claim 1, wherein the carboxylic acid compound is a monofunctional compound having a hydrocarbon group. 16 . The thermal interface material of claim 15 , wherein the molecular weight of the monofunctional compound is in the range of 50 g / mol to 400 g / mol. 17 . The thermal interface material of claim 1 , wherein the pKa of the carboxylic acid compound is in the range of 2 to 9.

18. The thermal interface material of claim 1, comprising both the carboxylic acid compound and the thiol compound.

19. The thermal interface material according to claim 1, wherein the amount of the filler component is 500 parts by weight or more relative to 100 parts by weight of the polyurethane.

20. The thermal interface material of claim 1, further comprising a plasticizer.

21. A product comprising a heating element and a thermal interface material according to any one of claims 1 to 20, The thermal interface material is adjacent to the heat generating element.

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