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 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 thereof.

Description

Technical Field

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0116477, 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 such as batteries that require thermal management increases, the importance of heat dissipation materials such as thermal interface materials (TIM) has also increased. 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 (for example, 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] Heat dissipation materials are basically required to have excellent thermal conductivity, and are also required to have other functions depending on the application. For example, depending on the application, the heat dissipation material may be required to exhibit low adhesion to a specific adherend and high thermal conductivity.

[0006] For example, when a component in a product that contacts the heat dissipation material 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, the polyurethane material is a material that exhibits high adhesive force to most adherends.

[0009] Methods for reducing the adhesive force of materials exhibiting high adhesive force include methods of blending components called so-called plasticizers. However, plasticizers formulated in large quantities for the purpose of controlling adhesive force have 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 is performed in which the heat dissipation material is applied to a desired position before curing and then cured. However, even after the heat dissipation material is applied, it is necessary to replace the parts in contact with the heat dissipation material in the product, or to 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, so there is a problem that the time available for replacement or position change is shortened.

[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 cannot 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. One purpose of the present application is that the curable composition or the thermal interface material, etc., show low adhesion to a given adherend while showing 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 the state of minimizing its use ratio 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, when the measurement temperature affects the result, unless otherwise specified, 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, when the measurement pressure affects the result, unless otherwise specified, 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 referred to as a resin in the art, or a composition not comprising a resin but comprising a component capable of forming a resin by a curing reaction or the like. Therefore, in this specification, the scope of the term resin or resin component includes not only components generally referred to as resins, but also components capable of forming a resin by a curing reaction and / or a polymerization reaction.

[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 and 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.); and 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-based or 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 cured body that can show low adhesion. Such a resin composition can be a polyurethane composition. Polyurethane is considered to be 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 such a 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, while not using a component such as a plasticizer that reduces adhesion or minimizing the amount used, low adhesion can also be achieved for the polyurethane material. Therefore, in the present application, such a material can be provided: it solves the problem of high adhesion that is not required according to the use while utilizing the advantages of the polyurethane material.

[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 2The 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 / mm 2 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 product whose adhesive force to aluminum is substantially unmeasurable. Therefore, the adhesive force to aluminum may be less than or equal to any of the above upper limits, and at the same time 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 solidified body to the polyester may be 100 gf / cm or less. In another example, the upper limit of the adhesive force of the resin composition or its solidified body to the polyester may 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 solidified body to the polyester may 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 cured product to polyester can be about 0gf / cm, 2gf / cm, 4gf / cm, 6gf / cm, 8gf / cm, 10gf / cm, 12gf / cm, 14gf / cm, 16gf / cm, 18gf / cm, 20gf / cm, 25gf / cm, 30gf / cm, 35gf / cm, 40gf / cm, 45gf / cm, 50gf / cm, 55gf / cm or 60gf / cm. The resin composition or its cured product may not substantially show adhesion to polyester. The adhesion of the resin composition or its cured product to 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 cured product to polyester can be measured in the manner described in the embodiments of this specification.

[0032] The resin composition or its cured body can show excellent thermal conductivity. For example, the lower limit of the thermal conductivity of the resin composition or its cured body can also be about 1.2W / mK, 1.4W / mK, 1.6W / mK, 1.8W / mK, 2.0W / mK, 2.2W / mK, 2.4W / mK or 2.6W / mK. The 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 the resin composition or its cured body can also be about 10W / mK, 9W / mK, 8W / mK, 7W / mK, 6W / mK, 5W / mK, 4W / mK or 3W / mK. The 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 a 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, according to the application, 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. The upper limit of the Shore OO hardness of the resin composition or its cured body can be 150, 140, 130, 120, 110, 100, 90 or 85. The Shore OO hardness can be less than or equal to any one of the above upper limits. The lower limit of the Shore OO hardness can be 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80 or 85. The Shore OO hardness can be greater than or equal to any one of the above lower limits. The Shore OO hardness can also be in the range of any one of the above upper limits to any one of the above lower limits. The hardness of such a resin composition or its cured body can be measured by the method disclosed in the embodiment described below.

[0034] Resin combination or its cured body can also show appropriate 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 or 9.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, as measured according to ASTM D149, the dielectric breakdown voltage of the resin composition or its cured body 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 considered 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 rating in a UL94V test (vertical burning test). Therefore, depending on the application of the resin composition, stability may be ensured against fire and other accidents of concern.

[0037] The specific gravity of the resin composition or its cured product 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 product 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 method of applying a filler having a low specific gravity or applying a surface-treated filler, etc.

[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, and the range may be, for example, less than 5%, less than 3%, or less than about 1%. Since the shrinkage is more favorable as the value decreases, 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 within the scope that can show the above-mentioned effect, and the scope 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. The stability at high temperatures can be further improved by such characteristics. 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, this means that since 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 polymeric 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] The polyfunctional compound may be referred to as a polyol compound in the present specification. There is no particular limitation on the number of hydroxyl groups contained in the polyfunctional compound (polyol compound). 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 may be expressed by 1 H NMR, where the hydroxyl number can be based on 1 The peaks in the 3 ppm to 4 ppm region of H NMR 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 a linear or branched hydrocarbon group having three or more carbon atoms at its 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. 1 H NMR determines whether a reactive compound contains hydrocarbon groups, where the presence and number of hydrocarbon groups can be based on 1 The oil-modified compound can be determined by the presence of a peak in the 4 ppm to 5 ppm region in HNMR. When the oil-modified compound is applied to form a polyurethane material, low adhesion to a specific material can be ensured without using a component that reduces adhesion, such as a plasticizer, or while minimizing the amount used.

[0046] The lower limit of the number of carbon atoms of the linear or branched hydrocarbon group included at the end of the oil-modified compound can be 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-mentioned lower limits. The upper limit of the number of carbon atoms can also be 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-mentioned upper limits. The number of carbon atoms can be in the range of any one of the above-mentioned lower limits to any one of the above-mentioned 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, and in this 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 such as 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 type of the hydrocarbon group being R in Formula 1 is as described above. Therefore, the contents concerning the carbon atom 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 in the form of at least some hydrogen atoms of hydrocarbon compounds such as alkanes, alkene or alkynes through hydroxyl and / or alkyl replacement. 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 be substituted on the same carbon atom, or can also be substituted 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 compound in question 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 concerned 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 case where there is no atom at the relevant position.

[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, and in this 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., a diol or a triol, etc.), and the skeleton of a caprolactone polyol can be formed by reacting a component comprising caprolactone with a polyol (e.g., a diol or a 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 may be represented by Formula 3 below.

[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; and 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 skeletons of the above formula 2 or 3 may be about 1 or 2, and the upper limit may be about 10, 9, 8, 7, 6, 5, 4, 3 or 2. The number of skeletons may 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 a main chain including a backbone of the above formula 2 or 3 is present and no other polymer chain is connected to the main chain, and the branched structure may be in a form in which a chain including a backbone of the above formula 2 or 3 is bonded as a side chain to the main chain including a backbone of the above formula 2 or 3. Here, in the branched structure, the number of chains including a backbone of the above formula 2 or 3 connected as a side chain 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 hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene or an alkyne are substituted with hydroxyl groups and / or a 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, and when R2 is a substituent of Formula 7, either one of X4 and 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 skeletons 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 the above formula 5 or 6 is present and no other polymer chain is connected to the main chain, and the branched structure may be in a form in which a chain including a skeleton of the above formula 5 or 6 is bonded as a side chain to the main chain including a skeleton of the above formula 5 or 6. Here, in the branched structure, the number of chains including a skeleton of the above formula 5 or 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 hydrogen atoms of a hydrocarbon compound such as an alkane, an alkene or an alkyne are substituted with hydroxyl groups and / or a 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 of 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 a suitable ratio. For example, the lower limit of the ratio of the oil-modified compound in the resin combination can be about 50 % by weight, 55 % by weight, 60 % by weight, 65 % by weight, 70 % by weight, 75 % by weight, 80 % by weight or 85 % by weight, and its upper limit can be about 95 % by weight, 90 % by weight, 85 % by weight, 80 % by weight or 75 % by weight. The 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 scope of any one in the above-mentioned lower limit to any one in 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, the content of the oil-modified compound is the content in the part in which the oil-modified compound exists. 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 other than the content of the solvent and the filler.

[0115] In another example, when the resin composition includes the filler component to be described below, the lower limit of the weight ratio of the oil-modified compound relative to 100 parts by weight of the filler component can be 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 can be 30 parts by weight, 28 parts by weight, 26 parts by weight, 24 parts by weight, 22 parts by weight, 20 parts by weight, 18 parts by weight, 16 parts by weight, 14 parts by weight, 12 parts by weight, 10 parts by weight or about 9 parts by weight. The ratio 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.

[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 all 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 all 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 or unsaturated fatty acids, and specifically, can be exemplified by 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 etc., but is not limited thereto.

[0118] The type of the polyol or alcohol compound to be reacted with the saturated 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 the reactive compound different from the oil-modified compound. In this case, the reactive compound does not include the above-mentioned hydrocarbyl (i.e., linear or branched hydrocarbyl with 3 or more carbon atoms). For convenience, such reactive compound can be referred to as non-oil-modified compound in this manual.

[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 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.

[0121] The non-oil modified compound may 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 may be a so-called carboxylic acid polyol or a caprolactone polyol. Such a polyol compound may be formed by a known method, for example, a carboxylic acid polyol may be formed by reacting a component comprising a carboxylic acid with a polyol (e.g., a diol or a triol, etc.), and a caprolactone polyol may be formed by reacting a component comprising caprolactone with a polyol (e.g., a diol or a triol, etc.). The carboxylic acid may 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 relevant skeleton number 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 skeleton number 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 a form in which a chain including a skeleton of the above formula 8 is bonded as a side chain 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 a side chain 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 their reaction products. At this time, 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 hydroxyls, such as trimethylolpropane. In addition, the dicarboxylic acid can be exemplified by adipic acid, terephthalic acid, isophthalic acid, or sebacic acid, etc. Such a polyol compound is known, for example, as Kuraray's product names 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, etc.

[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, about 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight or 95 parts by weight, and the upper limit thereof can be, for example, about 200 parts by weight, 190 parts by weight, 180 parts by weight, 170 parts by weight, 160 parts by weight, 150 parts by weight, 140 parts by weight, 130 parts by weight, 120 parts by weight, 110 parts by weight or 105 parts by weight. The ratio 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 less than or equal to any of the above upper limits, and at the same time be 3 or more.

[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, about 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight, and the upper limit 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 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 one suitable example, 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, the fourth reactive compound 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] In another example, the curable component may include a multifunctional compound (hereinafter, may be referred to as a fifth reactive compound) among the above-mentioned reactive compounds. At this time, the multifunctional compounds may each independently be an oil-modified compound or a non-oil-modified compound.

[0148] In the above case, the curable component may include a reactive compound having two hydroxyl groups (hereinafter, may be referred to as the sixth reactive compound) and a reactive compound having three or more hydroxyl groups (hereinafter, may be referred to as the seventh reactive compound) as a multifunctional compound. The upper limit of the number of hydroxyl groups contained in the seventh reactive compound may also be about 10, 9, 8, 7, 6, 5, 4 or 3 per molecule. The number of hydroxyl groups in the seventh reactive compound may be less than or equal to any of the above upper limits, and at the same time be 3 or more.

[0149] In this case, the lower limit of the weight ratio of the seventh reactive compound relative to 100 parts by weight of the sixth reactive compound can be, for example, about 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or 11 parts by weight, and the upper limit thereof can be, for example, about 20 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight, or 12 parts by weight. The ratio 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 from any of the above lower limits to any of the above upper limits.

[0150] The sixth reactive compound and the seventh reactive compound may each independently be an oil-modified compound or a non-oil-modified compound as described above.

[0151] In one suitable example, the sixth reactive compound among the sixth reactive compound and the seventh reactive compound may be an oil-modified compound.

[0152] In this case, the seventh reactive compound may be an oil-modified compound or a non-oil-modified compound, and in an appropriate example, the seventh reactive compound 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.

[0153] The resin composition may contain, for example, a curing agent that reacts with the curable component as an additional component.

[0154] 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 thereof 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 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.

[0155] 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.

[0156] 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.

[0157] 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 aforementioned 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.

[0158] 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.

[0159] For example, the resin composition may include polyisocyanate such that the 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.

[0160] Methods for calculating the equivalent ratio (OH / NCO) are known.

[0161] For example, if the resin composition is a two-component type, a curable component is contained in the main part, and polyisocyanate is contained in the curing agent part, the equivalent ratio OH / NCO can be calculated according to the following General Formula 1.

[0162] [General formula 1]

[0163]

[0164] 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 17 Da.

[0165] [General formula 2]

[0166] A=∑(W OH ×OH ％ )

[0167] In general formula 2, W OH is the weight ratio of the reactive compounds present in the main part, and OH ％ The weight ratio is W OH The ratio of hydroxyl groups contained in the reactive compound.

[0168] [General formula 3]

[0169] B=∑(W NCO ×NCO ％ )

[0170] In general formula 3, W NCO is the weight ratio of the polyisocyanate present in the curing agent part, and NCO ％ The weight ratio is W NCO The ratio of isocyanate groups contained in the polyisocyanate.

[0171] Here, W OHis the weight percent 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 ％ It is the % of hydroxyl groups contained in 1 mol 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.

[0172] Here, W NCO is the weight percent in the curing agent part of each polyisocyanate present in the curing agent part (based on the total weight of the curing agent part), and the NCO ％ It is the % of NCO groups 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 groups by the molar mass of the single polyisocyanate and then multiplying by 100.

[0173] In general formula 1, the Dalton mass is a constant.

[0174] 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.

[0175] The resin composition may further comprise a filler component. The term filler component means a component consisting of a filler, ie, a component comprising only a filler.

[0176] 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.

[0177] 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.

[0178] The average particle size of the filler of the present application means the particle size when the volume accumulation becomes 50% in the volume curve of the particle size distribution measured by laser diffraction, which can also be called the median diameter. That is, in the present application, the particle size distribution is obtained on a volume basis 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, and in another example, such an average particle size can be called the median particle size or D50 particle size.

[0179] Therefore, here, two kinds of 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.

[0180] 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. Therefore, 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] In one example, when the filler component contains 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 contained in the filler component, and when the filler component contains 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 contained in the filler component. In such a state, the particle size ratio may be satisfied.

[0188] 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 greater, 200 or greater, 210 or greater, 220 or greater, 230 or greater, or 235 or greater 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, approximately 100 or less, 95 or less, 90 or less, 85 or less, 80 or less, approximately 75 or less, 70 or less, 65 or less, or approximately 60 or less.

[0189] 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.

[0190] 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-mentioned range. In addition, the above-mentioned insulation characteristics, etc. can also be satisfied by applying ceramic fillers.

[0191] The upper limit of the ratio of the filler component in the 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 about 89.0 weight %, 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 about 88 weight %. 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 range of any one of the above-mentioned lower limit to any one of the above-mentioned upper limit.

[0192] 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 compound present in the curable component may be 500 parts by weight, 550 parts by weight, 600 parts by weight, 650 parts by weight, 700 parts by weight, 750 parts by weight, 800 parts by weight, 850 parts by weight, 900 parts by weight, 950 parts by weight, or about 1000 parts by weight, and the upper limit thereof may be about 2,000 parts by weight, 1,800 parts by weight, 1,600 parts by weight, 1,400 parts by weight, 1,200 parts by weight, 1,100 parts by weight, 1,000 parts by weight, 950 parts by weight, or about 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.

[0193] 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.

[0194] 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.

[0195] The filler component may include various types of fillers, and if necessary, in addition to the thermally conductive filler, for example, a carbon filler (eg, graphite), fumed silica, or clay, etc. may be used.

[0196] The resin composition may further contain necessary components in addition to the above-mentioned components.

[0197] In one example, the resin composition may further include a plasticizer. As described above, in the present application, low adhesion to a specific material may be ensured without using a plasticizer, but a small amount of a plasticizer may be used if necessary.

[0198] The type of plasticizer that can be applied is not particularly limited, and 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, etc. can be applied.

[0199] When a plasticizer is included, the ratio can be adjusted according to the purpose. For example, the lower limit of the ratio of the plasticizer may be 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, 12.5 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 The above ratio can be more 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.The above ratio can be considered to change in the composition or the intended use of whole resin combination.

[0200] 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 depending on the type of curing component. For example, when the resin composition is a polyurethane composition and the curable component is a component that forms a polyurethane, a polyurethanization catalyst may be used as a catalyst.

[0201] The polyurethane reaction catalyst is not particularly limited, and a known component can be used, and as an example thereof, 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 the catalyst, for example, a tin catalyst such as an organic tin catalyst can be used.

[0202] When comprising catalyst, ratio can be adjusted according to purpose.For example, relative to the gross weight of 100 weight portions of curable components or the reactive compound present in curable components, 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 0.5 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.

[0203] Resin combination may 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 begins to be 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 cure.

[0204] However, depending on the use of the resin composition, there may be a problem if the curing rate is too fast after the initiation of curing as described above.

[0205] 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 the curing rate modifier applied is not particularly limited. For example, a component that can show the effect of controlling the curing rate or show affinity by competitive reactions such as the curable components and catalysts included in the resin combination can be applied.

[0206] 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.

[0207] As the thiol compound, for example, a compound of the following Formula 9 can be used.

[0208] [Formula 9]

[0209] R1-R2-SH

[0210] 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.

[0211] 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.

[0212] 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 it 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.

[0213] 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 it 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.

[0214] 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, The heteroaryl group may be exemplified by 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 it 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.

[0215] 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 it 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.

[0216] 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 it 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.

[0217] 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).

[0218] The hydrocarbyl group of the thiol compound can be an alkyl, alkenyl or alkynyl group. At this time, the alkyl group can be an alkyl group having 1 to 30 carbon atoms, 4 to 30 carbon atoms, 8 to 30 carbon atoms, 8 to 26 carbon atoms, 8 to 22 carbon atoms, 8 to 18 carbon atoms or 8 to 14 carbon atoms, and the alkyl group can be linear or branched. The alkenyl or alkynyl group can be an alkenyl or alkynyl group having 2 to 30 carbon atoms, 4 to 30 carbon atoms, 8 to 30 carbon atoms, 8 to 26 carbon atoms, 8 to 22 carbon atoms, 8 to 18 carbon atoms or 8 to 14 carbon atoms, and the alkenyl or alkynyl group can be linear or branched.

[0219] 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.

[0220] If necessary, the alkane, alkene or alkyne may be optionally substituted with a substituent other than a thiol group, and in this case, the substituent may be exemplified by an alkoxy group having 1 to 4 carbon atoms and / or a silyl group (for example, the substituent represented by -Si(R3)3 of the above formula 9), etc., but is not limited thereto.

[0221] 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.

[0222] 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.

[0223] When comprising thiol compounds, ratio can be adjusted according to purpose.For example, relative to the gross weight of 100 parts by weight of curable component or reactive compound present in 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.

[0224] When the thiol compound and the catalyst are simultaneously contained in the polyurethane composition, their ratio may be controlled.

[0225] 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.

[0226] 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).

[0227] 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.

[0228] 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 atoms, 1 to 26 carbon atoms, 1 to 22 carbon atoms, 1 to 18 carbon atoms, 1 to 14 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 4 to 30 carbon atoms, 5 to 30 carbon atoms, 5 to 26 carbon atoms, 5 to 22 carbon atoms, 5 to 18 carbon atoms, 5 to 14 carbon atoms or 5 to 10 carbon atoms, and this alkyl 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.

[0229] 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.

[0230] 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.Described 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.

[0231] 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 its 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.

[0232] 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, oleic acid, or the like.

[0233] When comprising carboxylic acid compound, ratio can be adjusted according to purpose.For example, relative to the gross weight of 100 weight parts of curable component or the reactive compound present in curable component, the lower limit of the ratio of carboxylic acid compound can be about 0.001 weight part, 0.005 weight part, 0.01 weight part, 0.05 weight part, 0.1 weight part, 0.5 weight part, 1 weight part, 1.5 weight parts, 2 weight parts, 2.5 weight parts, 3 weight parts or 3.5 weight parts, and its upper limit can also be about 10 weight parts, 9 weight parts, 8 weight parts, 7 weight parts, 6 weight parts, 5 weight parts, 4 weight parts, 3 weight parts, 2 weight parts, 1 weight part, 0.9 weight part, 0.8 weight part, 0.7 weight part, 0.6 weight part, 0.5 weight part, 0.4 weight part, 0.3 weight part or 0.2 weight part. The ratio may 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. The above ratio may be changed in consideration of the composition or intended use of the entire resin composition.

[0234] When the carboxylic acid compound and the catalyst are simultaneously contained in the polyurethane composition, their ratio may be controlled.

[0235] 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 about 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, or 5.5, and an upper limit thereof may be about 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5.5, 5, 4.5, 4, 3.5, 3, 3.5, 2, 2.5, or 1. The ratio (C / U) may be greater than or equal to any of the above lower limits, less than or equal to any of the above upper limits, or in the range from any of the above lower limits to any of the above upper limits.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] As described above, the resin composition may be a one-component composition or a two-component composition.

[0240] In the case of a two-component composition, the above-mentioned respective components of the resin composition may be independently contained in physically separated main part and curing agent part.

[0241] 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).

[0242] 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.

[0243] 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.

[0244] 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.

[0245] For example, in the 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 of the above lower limits, less than or equal to any of the above upper limits, or in the range of any of the above lower limits to any of the above upper limits.

[0246] The ratio of the filler component in the main part can be defined as a ratio of 100 parts by weight relative to the total weight of the curable component of the main part or the reactive compound present in the curable component. For example, the lower limit of the ratio of the filler component can be 500 parts by weight, 550 parts by weight, 600 parts by weight, 650 parts by weight, 700 parts by weight, 750 parts by weight, 800 parts by weight, 850 parts by weight, 900 parts by weight, 950 parts by weight, or about 1,000 parts by weight, and the upper limit thereof can be 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 about 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.

[0247] In such cases, the upper limit of the ratio of the filler component in the curing agent portion 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.

[0248] The ratio of filler component in the curing agent part can also be defined as the ratio of the curing agent (polyisocyanate) in the curing agent part relative to 100 parts by weight. For example, the lower limit of the ratio of filler component can be 500 parts by weight, 550 parts by weight, 600 parts by weight, 650 parts by weight, 700 parts by weight, 750 parts by weight, 800 parts by weight, 850 parts by weight, 900 parts by weight, 950 parts by weight, 1,000 parts by weight, 1,500 parts by weight, 2,000 parts by weight, or about 2,500 parts by weight, and its upper limit can be 4,000 parts by weight, 3,500 parts by weight, or about 3,000 parts by weight. 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 range of any one of the above-mentioned lower limit to any one of the above-mentioned upper limit.

[0249] The main part and / or the curing agent part may contain a catalyst, a plasticizer, a flame retardant, etc. as other components as necessary.

[0250] 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 of any of the above lower limits to any of the above upper limits.

[0251] 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.

[0252] 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.

[0253] The present application also relates to a thermal interface material (TIM). The thermal interface material may be a cured product of a resin composition.

[0254] 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.

[0255] Therefore, the thermal interface material may include components included in the resin composition, or components derived from the components. For example, if the resin composition is a polyurethane composition, the thermal interface material may include polyurethane.

[0256] Polyurethane can be formed by reacting the above-mentioned reactive compound with a curing agent (polyisocyanate).Therefore, polyurethane can include units derived from reactive compounds.

[0257] 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 applied 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.

[0258] 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.

[0259] The specific method of configuring the product of the present application is not particularly limited, and if the resin composition or two-component composition of the present application or a cured body thereof is applied as a heat dissipation material, the product can be configured in various known ways.

[0260] Beneficial Effects

[0261] 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.

[0262] In the present application, the curable composition may also exhibit a precisely controlled curing rate and simultaneously have excellent curability.

[0263] 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

[0264] Figure 1 A diagram of a device for measuring load values.

[0265] Figure 2 The following are the analysis results of the reactive compounds synthesized in Preparation Example 1. DETAILED DESCRIPTION

[0266] Hereinafter, the present application will be specifically described through examples, but the scope of the present application is not limited by the following examples.

[0267] The cured body mentioned below is formed by mixing the main part of the resin composition prepared in a two-component type of the embodiment and the curing agent part so as to satisfy the OH / NCO equivalent ratio described in each embodiment, and then keeping the mixture at room temperature (25° C.) for about 24 hours.

[0268] In this example, physical properties were evaluated in the following manner.

[0269] 1. Thermal conductivity

[0270] 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 of the embodiment or comparative example are mixed at a volume ratio of 1:1 is placed in a mold with a thickness of about 7 mm, and 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.

[0271] 2. Measurement of Adhesion to Polyester

[0272] Adhesion to polyester is to evaluate the sample prepared by attaching PET (polyethylene terephthalate) film and aluminum plate. A film with a width of about 10mm and a length of about 200mm is used as the PET film, and an aluminum plate with a width and a length of 100mm 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 the length of about 100mm are attached to the aluminum plate via the resin composition. When the PET film is peeled off from the aluminum plate in the longitudinal direction while the aluminum plate of the sample is fixed, the adhesion is measured. Attachment is performed by applying a resin composition (a mixture of the main part and the curing agent part with a volume ratio of 1:1) to the aluminum plate to have a thickness of about 2mm after curing, and then the PET film is tightly 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.

[0273] 3. Measurement of adhesion to aluminum

[0274] Uncured resin composition (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 2cm and 7cm respectively in horizontal length and vertical length, with a width of 2cm and a length of about 2cm, and the aluminum substrate of 2cm and 7cm respectively in horizontal length and vertical length is attached to the coating again, and the resin composition is cured by keeping the state. Herein, two aluminum substrates are attached to form an angle of 90 degrees to each other. Hereinafter, when the upper aluminum substrate is fixed, the lower aluminum substrate is pressed at a speed of 0.5mm / min to measure the force when the 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 ​​the sample.

[0275] 4. Hardness measurement

[0276] The hardness of the cured body of the resin composition was measured according to ASTM D 2240 and JIS K 6253. It was performed using an ASKER durometer hardness device, wherein the initial hardness was measured by applying a load of 1 Kg or more (about 1.5 Kg) to the surface of the sample (resin layer) in a flat state, and after 15 seconds, the hardness was evaluated by determining a stable measured value.

[0277] 5. Measurement of curing rate

[0278] The curing rate of the resin composition was evaluated by the change in hardness over time. At this time, the hardness was measured in accordance with ASTM D 2240 and JIS K 6253 standards in the same manner as above.

[0279] The main part and the curing agent part were mixed at a volume ratio of 1:1, and a change in hardness over time was confirmed immediately after mixing while the mixture was kept at room temperature (about 25° C.) to measure a curing rate.

[0280] 6. Measurement of curvature radius

[0281] The curvature radius of the cured body was evaluated using cured bodies having a width, length and thickness of 1 cm, 10 cm and 2 mm, respectively. When the cured 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 cured body.

[0282] 7. Load rate measurement

[0283] Use as Figure 1 The loading rate (kgf) of the resin composition was evaluated using the apparatus disclosed in . Figure 1 The device is a device 1 in which two cartridges 2, 2a, 2b and a static mixer 5 are connected.

[0284] In the apparatus 1, as the cylinders 2, 2a, 2b, a cylinder (Sulzer, AB050-01-10-01) having a circular material injection portion with a diameter of 18 mm, a circular material discharge portion 4, 4a, 4b with a diameter of 3 mm, a height of 100 mm and an internal volume of 25 ml was used. As the static mixer 5, a stepped static mixer (Sulzer, MBH-06-16T) having a circular discharge portion 7 with a diameter of 2 mm and 16 elements was used.

[0285] As the pressurizing means 3, 3a, 3b (means for pushing the composition loaded in the cartridge) of the apparatus, TA (Texture Analyzer) was used.

[0286] When the main part is loaded into either of the two cylinders 2a, 2b, the curing agent part is loaded into the other cylinder, and then a certain force is applied thereto by the pressurizing device 3, 3a, 3b, the loading rate is measured while the main part and the curing agent part are mixed in the static mixer 5 via the first discharge part 4a, 4b and then discharged to the second discharge part 7.

[0287] The main part and the curing agent part respectively loaded into the two barrels 2a, 2b are pressurized at a constant speed of 1 mm / sec using TA (texture analyzer) 3a, 3b and injected into the static mixer 5, and while measuring the force applied to the pressurizing device from the time when the main part and the curing agent part injected into the mixer 5 are mixed in the mixer 5 and discharged for the first time from the discharge part 7, the force having the maximum value at the point where the force reaches its maximum value is designated as the load rate. When the force applied to the TA is measured in this manner, the force generally shows a tendency of continuously increasing and then decreasing or no longer increasing for the increased force, where the load rate is the maximum force before the decrease or the maximum force at the point where it no longer increases.

[0288] 8. Measurement of average particle size

[0289] 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. In the measurement, 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, which are analyzed using the Mie theory, thereby obtaining the D50 particle size. Through the above analysis, the distribution can be obtained by converting to the diameter of a sphere having 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.

[0290] 9. Module processability assessment

[0291] The resin composition (a mixture of the main part and the curing agent part in a volume ratio of 1:1) was applied to an aluminum plate in a square shape 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.

[0292] <Evaluation Criteria>

[0293] O: When the cured product of the resin composition peels off in a flake form without leaving any residue on the aluminum plate

[0294] X: When the cured product of the resin composition cannot be peeled off from the aluminum plate, or even if it is peeled off, a residue remains

[0295] 10. Evaluation of mixed status

[0296] The mixing state is measured using the same equipment as that for measuring the load rate (kgf). When the main part is loaded into either of the two cylinders 2a and 2b of the equipment, the curing agent part is loaded into the other, and then a certain force is applied to them with the pressing devices 3, 3a, 3b, visually observe the state of the mixture (a mixture of the main part and the curing agent part with a volume ratio of 1:1) when the main part and the curing agent part are mixed in the static mixer 5 via the first discharge parts 4a, 4b and then discharged to the second discharge part 7, and evaluate the mixing state according to the following criteria. When evaluating the mixing state, dyes are added to each of the main part and the curing agent part to have different colors.

[0297] <Evaluation criteria>

[0298] O: When the colors of the mixture of the main part and the curing agent part are evenly mixed and observed

[0299] X: When the colors of the mixture of the main part and the curing agent part are not evenly mixed and marbling etc. is observed

[0300] 11. Measurement of weight-average molecular weight

[0301] 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: Add the sample to be analyzed into a 5 mL vial, dilute it to a concentration of about 1 mg / mL with a THF (tetrahydrofuran) solvent, and then filter the standard sample for calibration and the analysis sample through a syringe filter (pore size: 0.45 μm). Use the ChemStation of Agilent technologies as the analysis program, and the weight-average molecular weight (Mw) can be obtained by comparing the elution time of the sample with the calibration curve.

[0302] <GPC measurement conditions>

[0303] Instrument: 1200 series of Agilent technologies

[0304] Column: Use TL Mix.A&B of Agilent technologies

[0305] Solvent: THF (tetrahydrofuran)

[0306] Column temperature: 35 °C

[0307] Sample concentration: 1 mg / mL, 200 μl injection

[0308] Standard sample: Polystyrene (MP: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

[0309] Preparation Example 1.

[0310] The oil-modified polyol compound (reactive compound) of the following formula A is prepared in the following manner.

[0311] [Formula A]

[0312]

[0313] In Formula A, n and m are each greater than 0, and the sum (n+m) is about 4.8.

[0314] Polycaprolactone polyol (Capa 3031, Perstorp) and isononanoic acid as saturated fatty acid are mixed with a weight ratio of 1:0.53 (Capa 3031: isononanoic acid). Subsequently, relative to the mixture of 100 parts by weight, catalyst (tin (II) (Sigma-Aldrich) of 2-ethylhexanoate) 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, and the reaction is carried out for 3 hours or more, then the pressure is reduced to 80 torr or lower, and xylene and unreacted product are removed. The reaction product is cooled and then filtered to obtain the target product (compound of formula A).

[0315] As a result of GPC analysis performed on the target product, the weight average molecular weight was about 876 g / mol. Figure 2 It is a figure which shows the result of GPC analysis of a target product.

[0316] Example 1.

[0317] Preparation of the main part

[0318] The oil-modified polyol compound of Preparation Example 1, a general polyol compound (Kuraray, F-2010), a polyurethane reaction catalyst (DBTDL, dibutyltin dilaurate), a carboxylic acid compound (2-EHA, 2-ethylhexanoic acid), a filler component and a plasticizer (diisononyl adipate) were mixed in a weight ratio of 90:10:0.63:0.86:1054:14.5 (Preparation Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer) to prepare a 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, a third alumina filler having an average particle size of about 1 μm, and aluminum hydroxide (ATH, aluminum hydroxide) having an average particle size of about 1 μm in a weight ratio of 62.5:21:10:6.5 (first alumina: second alumina: third alumina: ATH).

[0319] Preparation of curing agent

[0320] Polyisocyanate (Tolonate HDT-LV2, manufactured by Vencorex) was used as a curing agent. The main part was prepared by mixing the polyisocyanate, filler component and plasticizer (diisononyl adipate) in a weight ratio of 100:2516:119 (polyisocyanate:filler:plasticizer). As the filler component, the same component as in the main part was used.

[0321] 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 170.

[0322] Preparation of resin composition and cured product

[0323] The resin composition (curable composition) was prepared by separately preparing a main part and a curing agent part, and the main part and the curing agent part were mixed at a volume ratio of about 1:1, and then maintained at room temperature (about 25° C.) to form a cured body.

[0324] Example 2.

[0325] The main part was prepared in the same manner as in Example 1, except that the formulation ratio was changed to 90:10:0.63:1.26:1054:14.5 (Preparation Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent part, the resin composition and the cured body were prepared in the same manner as in Example 1.

[0326] Example 3.

[0327] The main part was prepared in the same manner as in Example 1, except that the formulation ratio was changed to 90:10:0.63:2.52:1054:14.5 (Preparation Example 1: F-2010:DBTDL:2-EHA:filler:plasticizer). The curing agent part, the resin composition and the cured body were prepared in the same manner as in Example 1.

[0328] Example 4.

[0329] The main part was prepared in the same manner as in Example 1, except that the formulation ratio was changed to 90:10:0.63:3.78:1054:14.5 (Preparation Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent part, the resin composition and the cured body were prepared in the same manner as in Example 1.

[0330] Example 5.

[0331] The main part was prepared in the same manner as in Example 1, except that the formulation ratio was changed to 90:10:0.23:0.69:1054:14.5 (Preparation Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent part, the resin composition and the cured body were prepared in the same manner as in Example 1.

[0332] Example 6.

[0333] The main part was prepared in the same manner as in Example 1, except that the formulation ratio was changed to 90:10:0.34:1.72:1055:14.7 (Preparation Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent part, the resin composition and the cured body were prepared in the same manner as in Example 1.

[0334] Example 7.

[0335] The main part was prepared in the same manner as in Example 1, except that the formulation ratio was changed to 90:10:0.57:2.86:1054:14.5 (Preparation Example 1: F-2010: DBTDL: 2-EHA: filler: plasticizer). The curing agent part, the resin composition and the cured body were prepared in the same manner as in Example 1.

[0336] Comparative Example 1.

[0337] The main part was prepared in the same manner as in Example 1, except that the carboxylic acid compound (2-EHA, 2-ethylhexanoic acid) was not used, and when preparing the main part, the formulation ratio was changed to 90:10:0.23:1054:14.5 (Preparation Example 1: F-2010: DBTDL: filler: plasticizer). The curing agent part, the resin composition and the cured body were prepared in the same manner as in Example 1.

[0338] The results of physical property evaluation for each of the above Examples and Comparative Examples are summarized in Table 1. In Table 1, hardness is hardness measured after a mixture of a main part and a curing agent part in a volume ratio of 1:1 is kept at room temperature (about 25° C.) for 24 hours.

[0339] In Table 1 below, Adhesion 2 is the adhesion to polyester, and Adhesion 1 is the adhesion to aluminum.

[0340] [Table 1]

[0341]

[0342] The results of evaluating the curing states of the resin compositions of the above Examples and Comparative Examples are summarized and described in Table 2 below.

[0343] The curing rate was evaluated by measuring the hardness over time while keeping a mixture of the main part and the curing agent part at a volume ratio of 1:1 at room temperature (about 25°C). In Table 2 below, H means hours. That is, 1H is the hardness at a time point when the mixture is kept for 1 hour after mixing.

[0344] [Table 2]

[0345]

[0346] From the results in Tables 1 and 2, it was confirmed that in the resin compositions of Examples, the curing reaction was delayed after the main part and the curing agent part were formulated due to the presence of the carboxylic acid compound.

[0347] Specifically, in the case of the embodiment, the time point when the hardness is confirmed after preparation is at least 2.5 hours or more, and the hardness at the first confirmation is not high, while in the case of Comparative Example 1, it can be known that rapid curing is achieved because high hardness is confirmed immediately after preparation.

[0348] From observing the results in Table 1, it can be understood that even when the curing reaction as above is delayed, the desired physical properties (thermal conductivity, low adhesion, flexibility, etc.) are ensured for the final cured body.

[0349] However, in the case of Comparative Example 1, high hardness was confirmed before 2 hours had passed after the main part and the curing agent part were prepared, which means that no curing delay was caused.

Claims

1. A curable composition comprising: a curable component comprising a reactive compound having a hydroxyl group, Carboxylic acid compounds, polyurethane reaction catalyst, and Filling component. 2 . The curable composition according to claim 1 , wherein the curable component comprises a first reactive compound having one hydroxyl group and a second reactive compound having two or more hydroxyl groups. 3 . The curable composition according to claim 2 , wherein the second reactive compound having two or more hydroxyl groups comprises a third reactive compound having two hydroxyl groups and a fourth reactive compound having three or more hydroxyl groups. 4 . The curable composition according to claim 1 , wherein the reactive compound comprises a branched hydrocarbon chain having 5 or more carbon atoms at a terminal end thereof. 5 . The curable composition of claim 3 , wherein the first reactive compound and the third reactive compound each comprise a branched hydrocarbon chain having 5 or more carbon atoms at each terminal.

6. The curable composition of claim 3, wherein the fourth reactive compound comprises a polycaprolactone polyol unit or an alkanediol unit; a polyol unit and a dicarboxylic acid unit. 7 . The curable composition according to claim 1 , wherein the carboxylic acid compound is a monofunctional compound having a hydrocarbon group. 8 . The curable composition according to claim 7 , wherein the molecular weight of the monofunctional compound is in the range of 50 g / mol to 400 g / mol. 9 . The curable composition of claim 1 , wherein the pKa of the carboxylic acid compound is in the range of 2 to 9. 10 . The curable composition according to claim 1 , wherein the carboxylic acid compound is included in an amount of 0.1 parts by weight to 6 parts by weight relative to 100 parts by weight of the curable component.

11. The curable composition of claim 1, wherein the urethanization catalyst is a tin catalyst. 12 . The curable composition according to claim 1 , wherein the urethanization reaction catalyst is included in an amount of 0.1 parts by weight to 3 parts by weight relative to 100 parts by weight of the curable component. 13 . The curable composition according to claim 1 , wherein a weight ratio of the carboxylic acid compound to the urethanization catalyst is 1 or more. 14 . The curable composition according to claim 1 , which forms a cured body having a thermal conductivity of 2.0 W / mK or more.

15. The curable composition according to claim 1, wherein the curable composition has an adhesion to aluminum of 0.15 N / mm 2 or smaller solidified body.

16. The curable composition according to claim 1, which forms a cured body having an adhesion to polyester of 100 gf / cm or less. 17 . The curable composition according to claim 1 , which forms a cured body having a Shore OO hardness of 95 or less.

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

19. The curable composition according to claim 1, comprising the filler component in an amount of 500 parts by weight or more relative to 100 parts by weight of the curable component.

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

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

22. A product comprising a heating element and a thermally conductive material, The thermally conductive material is present adjacent to the heat generating element, and the thermally conductive material comprises a cured body of the curable composition according to claim 1 or the two-component composition according to claim 20.

Images