Curable composition

Abstract

The present specification discloses a curable composition. The curable composition can exhibit excellent storage stability without viscosity change or viscosity non-uniformity caused by sedimentation of a filler, even while containing the filler at an excessive amount in order to achieve high thermal conductivity. The curable composition can exhibit both high thermal conductivity and storage stability even while using a hydroxide filler as a filler. The present specification discloses uses of the curable composition.

Description

curable composition

[0001] This application claims the benefit of priority to Republic of Korea Patent Application No. 10-2023-0190434, dated December 22, 2023, the entire contents of which are incorporated herein by reference.

[0002] The present specification discloses a curable composition and its use.

[0003] There are cases where a thermally conductive filler is mixed into the resin component and used as a thermally conductive material such as TIM (Thermal Interface Material).

[0004] In general, the more filler the material contains, the higher the thermal conductivity, so an excessive amount of filler is mixed with the resin component depending on the intended use.

[0005] For example, Patent Document 1 discloses the application of a material manufactured by mixing a thermally conductive filler into a resin component to a battery, wherein in an embodiment, the material includes 85 wt% or more of a thermally conductive filler.

[0006] Typically, fillers have a high density relative to the resin component. Therefore, when materials containing thermally conductive fillers are stored, the filler tends to settle along the direction of gravity. This filler settling can cause changes in the material's viscosity or uneven viscosity, reducing the processability of the material's application. Furthermore, when applied as a thermally conductive material, it can also result in a decrease in the material's thermal conductivity and its uniformity.

[0007] The risk of these problems increases as the content of fillers in the material increases.

[0008] Among fillers known as thermally conductive fillers, hydroxide fillers, such as aluminum hydroxide, have lower density and flame retardancy compared to other fillers, making them suitable for applications requiring lightweight properties and flame retardancy. However, hydroxide fillers exhibit inferior thermal conductivity compared to other known thermally conductive fillers. Therefore, when using hydroxide fillers, their content must be further increased to secure the desired thermal conductivity, and this increased content further increases the risk of the problems described above.

[0009] [Prior Art Literature]

[0010] [Patent Document]

[0011] (Patent Document 1) Republic of Korea Patent No. 10-2393127

[0012] The present specification discloses a curable composition. The purpose of the present specification is to disclose a curable composition that can prevent viscosity changes or viscosity unevenness by preventing sedimentation of the filler, etc., even when containing an excessive amount of filler to achieve high thermal conductivity, and to ensure storage stability. Another purpose of the present specification is to disclose a curable composition that can simultaneously secure high thermal conductivity and storage stability while using a hydroxide filler as a filler.

[0013] The present specification discloses uses of the curable composition.

[0014] Among the properties mentioned in this specification, properties whose results are affected by the measurement temperature are properties measured at room temperature unless otherwise specifically stated.

[0015] The term room temperature means the natural temperature that has not been heated or cooled, for example, any temperature within the range of about 10°C to 30°C, for example, a temperature of about 23°C or about 25°C.

[0016] Unless otherwise specified in this specification, the unit of temperature is ℃.

[0017] Among the properties mentioned in this specification, if the measurement pressure affects the result, the property is a property measured at atmospheric pressure unless otherwise specified.

[0018] The term atmospheric pressure refers to the natural pressure that is neither pressurized nor depressurized, and is usually a pressure in the range of about 700 mmHg to 800 mmHg.

[0019] Among the properties mentioned in this application, properties whose results are affected by measured humidity are properties measured at standard humidity unless specifically stated otherwise.

[0020] Standard humidity refers to a relative humidity (RH%) within a range of about 50% to 60%, for example, a relative humidity (RH%) of about 50%, 55%, or 60%.

[0021] In this specification, the average particle diameter of the filler refers to the so-called D50 particle diameter (Median Diameter), unless otherwise specified. The method for measuring the D50 particle diameter is outlined in "2. Measurement of Average Particle Diameter" in the Examples section of this specification.

[0022] In this specification, the terms spherical filler and non-spherical filler are concepts distinguished by circularity, and the category of non-spherical fillers may include square, amorphous, disc-shaped or needle-shaped fillers.

[0023] In this specification, a filler having a circularity of about 0.9 or more or 0.95 or more may be designated as a spherical filler, and a filler having a circularity of less than 0.95 or less than 0.9 may be designated as a non-spherical filler. The sphericity can be confirmed through particle shape analysis of the filler. The sphericity of a filler, which is a three-dimensional particle, is defined as the ratio (S' / S) of the surface area (S) of the filler and the surface area (S') of a sphere having the same volume as the filler. For actual fillers, circularity is generally used. The circularity is expressed as the ratio of the boundary (P) of a two-dimensional image of the actual filler to the boundary of a circle having the same area (A) as the image, and is obtained by the following formula.

[0024] <Circularity formula>

[0025] Circularity = 4πA / P 2

[0026] The above circularity is expressed as a value from 0 to 1, with a perfect circle having a value of 1, and the more irregular the shape, the lower the value. In this specification, the sphericity value is the average value of the circularity measured by Marvern's particle shape analysis equipment (FPIA-3000).

[0027] The present specification discloses a curable composition. The term "curable composition" refers to a composition capable of being cured. The term "curing" refers to a phenomenon in which the viscosity and / or hardness of the composition increases through a chemical and / or physical reaction or interaction.

[0028] The curable composition may be a solvent-based or solvent-free composition. The term solvent-based composition refers to a composition comprising a solvent (aqueous or organic solvent), and the solvent-free composition refers to a composition substantially free of the solvent. In the solvent-free composition, the upper limit of the solvent content may be about 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.001 wt%, 0.0005 wt%, or 0.0001 wt%, and the lower limit may be about 0 wt%. The solvent content in the solvent-free composition may be within a range that is less than or equal to any one of the above-described upper limits; or within a range that is less than or equal to any one of the above-described upper limits and greater than or equal to the above-described lower limit.

[0029] The curable composition may be an energy ray (e.g., ultraviolet) curable composition, a moisture-curable composition, a heat-curable composition, or a room temperature-curable composition. When the curable composition is an energy ray-curable composition, curing of the curable composition may be performed by irradiating the composition with an energy ray such as ultraviolet rays. When the curable composition is a moisture-curable composition, curing of the curable composition may be performed by maintaining the composition under an appropriate moisture content. When the curable composition is a heat-curable composition, curing of the curable composition may be performed by applying an appropriate heat to the composition. Alternatively, when the curable composition is a room temperature-curable composition, curing of the curable composition may be performed by maintaining the curable composition at room temperature.

[0030] In one example, the curable composition may be a room temperature curable composition, and in particular, may be a composition in which curing occurs by maintaining the composition at room temperature without application of external energy such as energy rays or application of excessive moisture.

[0031] The curable composition may be a one-component or two-component composition, and in some cases may be a part of the two-component composition.

[0032] The term one-component composition means a composition in which all components necessary for curing are mixed together as is known, and which cures when certain conditions (e.g., application of heat or energy rays, exposure to moisture, etc.) are satisfied.

[0033] The term two-component composition refers to a composition in which the components necessary for curing are physically separated (e.g., separated into a main component and a curing agent part), and the separated components are mixed and cured by exposure to a curable environment.

[0034] The above curable composition can exhibit excellent storage stability even when it contains an excessive amount of filler, as described below.

[0035] The above excellent storage stability can be reflected as △V in Equation 1 below.

[0036] [Formula 1]

[0037] △V = 100 × (V L -V U ) / V U

[0038] V in Equation 1 L and V U These are the lower and upper viscosities of the curable composition, which were checked after each curable composition was injected into a 30 mL dispenser syringe having a diameter of 26.2 mm and a length of 130 mm, the dispenser syringe was maintained in a vertical position, and maintained at 25°C for 30 days.

[0039] The method for obtaining △V of the above equation 1 is specifically described in “9. Storage stability evaluation” of the Examples section of this specification.

[0040] The smaller the absolute value of △V in the above equation 1, the less likely it is that the filler will settle in the vertical storage state and a uniformly mixed state can be maintained.

[0041] The lower limit of the absolute value of △V in Equation 1 may be about 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, or 6.5%, and the upper limit may be about 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or 0.5%. The absolute value of △V may be within a range that is less than or equal to any one of the above-described upper limits; or within a range that is less than or equal to any one of the above-described upper limits and greater than or equal to any one of the above-described lower limits.

[0042] △V in Equation 1 can be positive or negative. Typically, when the vertical state is maintained, the lower viscosity (V) of the curable composition L ) is the upper viscosity (V U ) is likely to be larger than the contrast, so △V is generally likely to be positive, but it can also be negative.

[0043] The above curable composition can exhibit excellent storage stability even when it contains an excessive amount of filler to secure high thermal conductivity. For example, the lower limit of the thermal conductivity of the curable composition or the cured product of the curable composition may be about 2.5 W / m·K, 2.9 W / m·K, 3.0 W / m·K, 3.05 W / m·K, 3.1 W / m·K, 3.15 W / m·K or 3.2 W / m·K, and the upper limit may be about 50 W / m·K, 45 W / m·k, 40 W / m·k, 35 W / m·k, 30 W / m·k, 25 W / m·k, 20 W / m·k, 15 W / m·k, 10 W / m·K, 9 W / m·K, 8 W / m·K, 7 W / m·K, 6 W / m·K, 5 W / m·K, 4 W / m·K or 3 W / m·K. The above thermal conductivity may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above and equal to or greater than any one of the lower limits described above. The above thermal conductivity may be evaluated according to the method described in “1. Evaluation of Thermal Conductivity” in the Examples section of this specification.

[0044] The above curable composition may include at least a resin component and a filler component.

[0045] There is no particular limitation on the type of the above resin component. As the above resin component, various known components applicable to the formation of thermally conductive materials, such as so-called thermal interface materials (TIMs), can be used.

[0046] Examples of such ingredients include polyurethane ingredients, silicone ingredients, epoxy ingredients, or acrylic ingredients.

[0047] In one example, the resin component may be a polyurethane component. The term polyurethane component includes known polyurethanes (polymer compounds bonded with urethane bonds) or components capable of forming the polyurethane through chemical and / or physical reactions.

[0048] As components capable of forming the above polyurethane, so-called polyols and polyisocyanates are known. These components can form the polyurethane through a urethane reaction. In some cases, a so-called chain extender can also react with the polyol and / or polyisocyanate to form the polyurethane. When the curable composition is a main component or a curing agent part of a two-component composition, the curable composition may include a portion of the polyol, polyisocyanate, and an optional chain extender.

[0049] As used herein, the term "polyol" refers to a compound containing two or more hydroxyl groups. For example, a compound containing two hydroxyl groups is typically called a diol, and a compound containing three hydroxyl groups is typically called a triol. These diols and triols are also types of polyols.

[0050] The lower limit of the number of hydroxyl groups of the polyol may be 2 or 3, and the upper limit may be 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of the hydroxyl groups may be within a range that is less than or equal to any one of the upper limits described above; within a range that is greater than or equal to any one of the lower limits described above; or within a range that is less than or equal to any one of the upper limits described above and greater than or equal to any one of the lower limits described above.

[0051] The polyol may have a hydroxyl value (OH value) within an appropriate range. The hydroxyl value of the polyol may be measured according to ASTM E 1899-08. The lower limit of the hydroxyl value may be about 100 mgKOH / g, 150 mgKOH / g, 200 mgKOH / g, or 250 mgKOH / g, and the upper limit may be about 500 mgKOH / g, 450 mgKOH / g, 400 mgKOH / g, 350 mgKOH / g, or 300 mgKOH / g. The hydroxyl value may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0052] The polyol may have an acid value within an appropriate range. A method for measuring the acid value of the polyol is described in the Examples section of the present specification. The lower limit of the acid value may be about 0 mgKOH / g, and the upper limit may be about 5 mgKOH / g, 4 mgKOH / g, 3 mgKOH / g, 2 mgKOH / g, 1 mgKOH / g, 0.9 mgKOH / g, 0.8 mgKOH / g, 0.7 mgKOH / g, 0.6 mgKOH / g, 0.5 mgKOH / g, 0.4 mgKOH / g, or 0.3 mgKOH / g. The acid value is within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0053] The lower limit of the molecular weight or weight average molecular weight of the polyol may be about 100 g / mol, 150 g / mol, 200 g / mol, 250 g / mol, 300 g / mol, 350 g / mol or 400 g / mol, and the upper limit may be about 1,000 g / mol, 900 g / mol, 800 g / mol, 700 g / mol, 600 g / mol or 500 g / mol. The molecular weight or weight average molecular weight may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0054] As the polyol, any known polyol can be used without any particular limitation. Polyols that form polyurethane include polyether polyols and polyester polyols, and such polyols can be used in the curable composition.

[0055] Polyether polyols generally include (poly)ethylene glycol, diethylene glycol, (poly)propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,2-ethylhexyldiol, 1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, (poly)ethylenetriol, diethylenetriol, (poly)propylenetriol, glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,3,4-hexanetriol, 1,3,6-hexanetriol units and / or trimethylolpropane. It is known.

[0056] In one example, the polyol may be a polyester polyol. Known polyester polyols include so-called carboxylic acid-based polyols or caprolactone-based polyols, and these polyols may be used as the resin component alone or in a mixture of two or more.

[0057] For example, the polyester polyol may be a polyol represented by the following chemical formula 1 or 2.

[0058] [Chemical Formula 1]

[0059]

[0060] [Chemical Formula 2]

[0061]

[0062] In chemical formulas 1 and 2, X is a dicarboxylic acid-derived unit, Y is a polyol-derived unit (e.g., a triol or diol unit), and n and m are arbitrary numbers.

[0063] The above dicarboxylic acid-derived unit is a unit formed by a dicarboxylic acid reacting with a polyol and a urethane, and the polyol-derived unit is a unit formed by a polyol reacting with a dicarboxylic acid or caprolactone and a urethane.

[0064] That is, when the hydroxyl group of the polyol and the carboxyl group of the dicarboxylic acid react, an ester bond is formed as water (H2O) molecules are eliminated by the condensation reaction. X in chemical formula 1 means a portion excluding the ester bond portion after the dicarboxylic acid forms an ester bond by the condensation reaction, and Y also means a portion excluding the ester bond after the polyol forms an ester bond by the condensation reaction, and the ester bond is indicated in chemical formula 1.

[0065] Y in chemical formula 2 also represents the portion excluding the ester bond formed after the polyol forms an ester bond with caprolactone.

[0066] In the case where the polyol-derived unit of Y in chemical formulas 1 and 2 is a unit derived from a polyol containing three or more hydroxyl groups, such as a triol unit, a structure in which the Y portion in the structure of the chemical formula is branched can be implemented.

[0067] The type of the dicarboxylic acid-derived unit of X in chemical formula 1 is not particularly limited. For example, the unit may be any one unit or two or more types of units selected from the group consisting of a phthalic acid unit, an isophthalic acid unit, a terephthalic acid unit, a rimellitic acid unit, a tetrahydrophthalic acid unit, a hexahydrophthalic acid unit, a tetrachlorophthalic acid unit, an oxalic acid unit, an adipic acid unit, an azelaic acid unit, a sebacic acid unit, a succinic acid unit, a malic acid unit, a glutaric acid unit, a malonic acid unit, a pimelic acid unit, a suberic acid unit, a 2,2-dimethylsuccinic acid unit, a 3,3-dimethylglutaric acid unit, a 2,2-dimethylglutaric acid unit, a maleic acid unit, a fumaric acid unit, an itaconic acid unit, and a fatty acid unit.

[0068] In chemical formulas 1 and 2, the type of polyol-derived unit of Y is not particularly limited. For example, the unit may be any one or two or more units selected from the group consisting of an ethylene glycol unit, a propylene glycol unit, a 1,2-butylene glycol unit, a 2,3-butylene glycol unit, a 1,3-propanediol unit, a 1,3-butanediol unit, a 1,4-butanediol unit, a 1,6-hexanediol unit, a neopentyl glycol unit, a 1,2-ethylhexyldiol unit, a 1,5-pentanediol unit, a 1,10-decanediol unit, a 1,3-cyclohexanedimethanol unit, a 1,4-cyclohexanedimethanol unit, a glycerin unit, and a trimethylolpropane unit.

[0069] In chemical formula 1, n and m are arbitrary numbers, and their ranges can be selected in consideration of the desired properties.

[0070] For example, the lower limit of n may be about 2 or 3, and the upper limit may be about 10, 9, 8, 7, 6, or 5. The n may be within a range that is less than or equal to any one of the upper limits described above; within a range that is greater than or equal to any one of the lower limits described above; or within a range that is less than or equal to any one of the upper limits described above and greater than or equal to any one of the lower limits described above.

[0071] For example, the lower limit of m may be about 2 or 3, and the upper limit may be about 10, 9, 8, 7, 6, or 5. The m may be within a range that is less than or equal to any one of the upper limits described above; within a range that is greater than or equal to any one of the lower limits described above; or within a range that is less than or equal to any one of the upper limits described above and greater than or equal to any one of the lower limits described above.

[0072] As the above resin component, polyisocyanate may be applied. The term polyisocyanate may mean a compound having two or more isocyanate groups. The lower limit of the number of isocyanate groups of the polyisocyanate may be about 2 or 3, and the upper limit may be about 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of the isocyanate groups may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0073] As polyisocyanates, those commonly used in the industry (e.g., those commonly used for forming polyurethane) can be used without particular limitation. For example, diisocyanates (compounds having two isocyanate groups) and / or polyisocyanates having three or more isocyanate groups can be used as polyisocyanates, although there are no particular limitations.

[0074] When the curable composition is the main part or the curing agent part of the two-component composition described above, the resin component may include at least one selected from the group consisting of the polyol and polyisocyanate.

[0075] The content of the resin component in the curable composition may be determined based on the filler component included in the resin component. For example, the lower limit of the weight ratio of the resin component to 100 parts by weight of the filler component of the curable composition may be about 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, or 8 parts by weight, and the upper limit may be about 100 parts by weight, 95 parts by weight, 90 parts by weight, 85 parts by weight, 80 parts by weight, 75 parts by weight, 70 parts by weight, 65 parts by weight, 60 parts by weight, 55 parts by weight, 50 parts by weight, 45 parts by weight, 40 parts by weight, 35 parts by weight, 30 parts by weight, 25 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight, or 9 parts by weight. The weight ratio may be within a range that is greater than or equal to any one of the lower limits described above; or within a range that is less than or equal to any one of the upper limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0076] When the polyol and polyisocyanate are included simultaneously as resin components, the ratio between the two components is not limited, and for example, the ratio can be controlled so that the two components can react to form polyurethane. In one example, when the two components are included simultaneously, the ratio between them can be adjusted in consideration of the ratio (OH / NCO) of the number of moles of hydroxyl groups (OH) included in the polyol to the number of moles of isocyanate groups (NCO) included in the polyisocyanate. For example, the lower limit of the ratio OH / NCO can be about 0.01, 0.05, 0.1, 0.5, or 1, and the upper limit can be about 100, 50, 25, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1. The above ratio OH / NCO may be within a range that is equal to or greater than any one of the lower limits described above and less than or equal to any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0077] In one example, when the curable composition is a subject part or a curing agent part of a two-component composition, the subject part may include a polyol among the curable compounds, and the curing agent part may include a polyisocyanate among the curable compounds.

[0078] The curable composition includes a filler component along with the resin component. The term "filler component" refers to a component consisting solely of fillers. Therefore, for example, all fillers included in the curable composition may be combined to form the filler component.

[0079] In the curable composition, the lower limit of the weight ratio of the filler component may be about 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 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%, 88 wt%, 89 wt% or 90 wt%, and the upper limit may be about 99 wt%, 98 wt%, 97 wt%, 96 wt%, 95 wt%, 94 wt%, 93 wt% or 92 wt%. The weight ratio of the filler component is within a range that is equal to or greater than any one of the lower limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0080] In the above curable composition, even when an excessive amount of filler component is included to secure desired properties such as thermal conductivity, the excellent storage stability described above can be secured.

[0081] The above filler component may include a thermally conductive filler or may be a thermally conductive filler component. The term thermally conductive filler or thermally conductive filler component refers to a filler or filler component that enables the curable composition or the cured product of the curable composition to exhibit the thermal conductivity described above through the filler or filler component.

[0082] Examples of fillers that can form the above filler component include, but are not limited to, oxide fillers such as aluminum oxide (alumina), magnesium oxide, beryllium oxide, or titanium oxide; nitride fillers such as boron nitride, silicon nitride, or aluminum nitride; carbide fillers such as silicon carbide; hydroxide fillers such as aluminum hydroxide or magnesium hydroxide; metal fillers such as copper, silver, iron, aluminum, or nickel; metal alloy fillers such as titanium; or silicon powder such as quartz, glass, or silica. In addition, when securing insulating properties is taken into consideration, the application of carbon fillers such as graphite or activated carbon can also be considered.

[0083] One or more of the above fillers may be included in the filler component.

[0084] The above filler may include at least a hydroxide filler among the fillers described above. Hydroxide fillers have excellent insulation and flame retardancy properties, and their lower density compared to other fillers makes them advantageous for forming lighter materials. However, even when using such hydroxide fillers, the desired high thermal conductivity and storage stability can be achieved simultaneously.

[0085] The lower limit of the content of the hydroxide filler in the above filler component may be about 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt% or 32 wt%, and the upper limit may be, for example, about 50 wt%, 45 wt%, 40 wt%, 35 wt%, 34 wt%, 33 wt%, 32 wt%, 31 wt%, 30 wt%, 28 wt% or 26 wt%. The weight ratio may be within a range that is equal to or greater than any one of the above-described lower limits; or within a range that is equal to or less than any one of the above-described upper limits; or within a range that is equal to or greater than any one of the above-described lower limits and equal to or less than any one of the above-described upper limits.

[0086] The filler component may be adjusted to secure the above storage stability, flame retardancy, thermal conductivity, etc.

[0087] For example, the weighted average BET specific surface area of ​​the filler component can be adjusted. The weighted BET specific surface area is a weight-weighted average value calculated by considering the mixing weight ratio of the BET specific surface areas of all the fillers mixed when forming the filler component by mixing a plurality of fillers. For example, when the filler component is formed by mixing a filler (1) having a BET specific surface area of ​​B1 and a filler (2) having a BET specific surface area of ​​B2 in a weight ratio of W1:W2 (1:2), the weighted average BET specific surface area is a value obtained by (B1×W1+B2×W2) / (W1+W2). The method for obtaining the BET specific surface area of ​​each filler is described in “5. Evaluation of the specific surface area of ​​the filler” in the Examples section of this specification.

[0088] The smaller the BET surface area of ​​the filler component, the lower the degree of interaction between the filler component and other components such as the resin component, and conversely, the higher the BET surface area, the higher the degree of interaction between the filler component and other components such as the resin component, and accordingly, the BET surface area can be adjusted to an appropriate level in consideration of the purpose.

[0089] The lower limit of the weighted average BET surface area of ​​the above filler component is 0.75 m 2 / g, 0.80 m 2 / g, 0.85 m 2 / g, 0.90 m 2 / g, 0.95 m 2 / g, 1.00 m 2 / g or 0.17 m 2 / g can be about, and its upper limit is 10 m 2 / g, 9.5 m 2 / g, 9 m 2 / g, 8.5 m 2 / g, 8 m 2 / g, 7.5 m 2 / g, 7 m 2 / g, 6.5 m 2 / g, 6 m 2 / g, 5.5 m 2 / g, 5 m 2 / g, 4.5 m 2 / g, 4 m 2 / g, 3.5 m 2 / g, 3 m 2 / g, 2.5 m 2 / g, 2 m 2 / g, 1.5 m 2 / g, 1.0 m 2 / g, 0.95 m 2 / g or 0.9 m 2 / g. The weighted average BET specific surface area may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0090] The weighted average BET surface area of ​​the hydroxide filler included in the above filler component can also be adjusted. The meaning of the weighted average BET surface area in the above is as described above. The lower limit of the weighted average BET surface area of ​​the hydroxide filler is 0.01 m 2 / g, 0.05 m 2 / g, 0.10 m 2 / g or 0.15 m 2 / g can be about, and its upper limit is 1 m 2 / g, 0.95 m 2 / g, 0.9 m 2 / g, 0.85 m 2 / g, 0.8 m 2 / g, 0.75 m 2 / g, 0.7 m 2 / g, 0.65 m 2 / g, 0.6 m 2 / g, 0.55 m 2 / g, 0.5 m 2 / g, 0.45 m 2 / g, 0.4 m 2 / g, 0.35 m 2 / g, 0.3 m 2 / g, 0.25 m 2 / g or 0.2 m 2 / g. The weighted average BET specific surface area may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0091] The above filler component may include a non-hydroxide filler in addition to the above hydroxide filler. In this case, the non-hydroxide filler means all fillers other than the hydroxide filler present in the filler component, and specific examples thereof include, but are not limited to, the above-mentioned oxide filler; nitride filler, carbide filler; metal filler; metal alloy filler; silicon powder; and / or carbon filler.

[0092] The weighted average BET surface area of ​​the non-hydroxide filler included in the above filler component can also be adjusted. The meaning of the weighted average BET surface area is as described above. The lower limit of the weighted average BET surface area of ​​the non-hydroxide filler is 0.4 m 2 / g, 0.6 m 2 / g, 0.8 m 2 / g, 1.0 m 2 / g, 1.2 m 2 / g or 0.3 m 2 / g can be about, and its upper limit is 10 m 2 / g, 9 m 2 / g, 8 m 2 / g, 7 m 2 / g, 6 m 2 / g, 5 m 2 / g, 4 m 2 / g, 3 m 2 / g, 2 m 2 / g or 1.5 m 2 / g. The weighted average BET specific surface area may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0093] The weighted average particle size of the above filler component can be adjusted. The weighted average particle size is a weight-weighted average value calculated by considering the mixing weight ratio of the average particle sizes of all the fillers mixed when forming the filler component by mixing multiple fillers. For example, when the filler (1) having an average particle size of D1 and the filler (2) having an average particle size of D2 are mixed in a weight ratio of W1:W2 (1:2), the weighted average particle size is a value obtained by (D1×W1+D2×W2) / (W1+W2).

[0094] The lower limit of the weighted average particle size of the above filler component may be about 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm, and the upper limit may be about 50 μm, 45 μm, 40 μm, 35 μm, or 30 μm. The weighted average particle size of the above filler component may be within a range that is less than or equal to any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0095] The weighted average particle size of the hydroxide filler included in the above filler component can be adjusted. The meaning of the weighted average particle size is as described above. The lower limit of the weighted average particle size of the hydroxide filler may be about 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm or 80 μm, and the upper limit may be about 200 μm, 190 μm, 180 μm, 170 μm, 160 μm, 150 μm, 140 μm, 130 μm, 120 μm, 110 μm, 100 μm, 90 μm, 85 μm or 80 μm. The weighted filler particle size is within a range that is equal to or greater than any one of the lower limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0096] The weighted average particle size of the non-hydroxide filler in the above filler component can be adjusted. The meaning of the weighted average particle size is as described above. The lower limit of the weighted average particle size of the non-hydroxide filler may be about 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, and the upper limit may be about 50 μm, 45 μm, 40 μm, 35 μm, 30 μm, 28 μm, 26 μm, 24 μm, 22 μm, 20 μm, 18 μm, 16 μm, 14 μm, 12 μm, 10 μm or 8 μm. The weighted average particle size is within a range that is equal to or less than any one of the upper limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0097] The weighted average particle size of the non-spherical filler contained in the above filler component can also be adjusted. The meaning of the weighted average particle size is as described above. The lower limit of the weighted average particle size of the non-spherical filler may be about 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, or 35 μm, and the upper limit may be about 42 μm, 41 μm, 40 μm, 39 μm, 38 μm, 37 μm, 36 μm, 35 μm, 34 μm, 33 μm, 32 μm, 31 μm, 30 μm, 29 μm, or 28 μm. The weighted filler particle size is within a range that is equal to or less than any one of the upper limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0098] The above filler component may include the non-spherical filler within a certain range. The lower limit of the content of the non-spherical filler in the above filler component may be about 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt% or 75 wt%, and the upper limit may be about 90 wt%, 85 wt%, 80 wt%, 75 wt% or 70 wt%. The weight ratio may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0099] The weighted average particle size of the spherical filler included in the filler component can be adjusted. The meaning of the weighted average particle size is as described above. The lower limit of the weighted average particle size may be about 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, or 20 μm, and the upper limit may be about 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, or 20 μm. The weighted filler particle size may be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0100] The above filler component can be manufactured, for example, by mixing two or more types of fillers having different average particle sizes. In this case, the upper limit of the types of fillers to be mixed may be about 10, 9, 8, 7, 6, 5, 4, or 3, and the lower limit may be 2. The types of fillers may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0101] In the above case, △W1 of the following formula 2 of the filler component can be adjusted.

[0102] [Formula 2]

[0103] △W1 = W other / W T

[0104] W in Equation 2 T is the weight of the filler with the smallest average particle size among the fillers mixed above, and W other is the weight W of the total weight of the filler component.T It is the value minus .

[0105] The lower limit of the above △W1 may be about 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7 or 1.8, and the upper limit may be about 5, 4.5, 4, 3.5, 3, 2.5, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1 or 1.0. The value of the above △W1 is within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0106] By formulating the filler component so that the above △W1 is within the above range, the desired high thermal conductivity and storage stability can be secured simultaneously. If △W1 is too small, thermal conductivity may not be effectively secured, and if △W1 is too large, there is a possibility that a difference in upper and lower viscosity may occur due to sedimentation of the filler component.

[0107] In the above case, △W2 of the following formula 3 of the filler component may be within a certain range.

[0108] [Formula 3]

[0109] △W2 = W F / W S

[0110] W in Equation 3 F is the weight of the filler with the largest average particle size among the mixed fillers, and W S is the weight of the filler with the second largest average particle size among the fillers being mixed.

[0111] The lower limit of △W2 in the above equation 3 may be about 0.1, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0, and the upper limit may be about 2, 1.5, 1.4, 1.3, 1.2, 1.1, or 1.0. The value of △W2 may be within a range that is equal to or greater than any one of the lower limits described above; within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0112] Among the fillers mixed to form the above filler component, the average particle diameter of the filler with the largest average particle diameter (hereinafter, large-diameter filler) can be adjusted. For example, the lower limit of the average particle diameter of the large-diameter filler can be about 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, or 80 μm, and the upper limit can be about 200 μm, 190 μm, 180 μm, 170 μm, 160 μm, 150 μm, 140 μm, 130 μm, 120 μm, 110 μm, 100 μm, 90 μm, 85 μm, or 80 μm. The average particle diameter is within a range that is equal to or greater than any one of the lower limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0113] The lower limit of the BET surface area of ​​the above large-diameter filler is 0.01 m 2 / g, 0.05 m 2 / g, 0.1 m 2 / g, 0.15 m 2 / g or 0.17 m 2 / g can be about, and its upper limit is 5 m 2 / g, 4.5 m 2 / g, 4 m 2 / g, 3.5 m 2 / g, 3 m 2 / g, 2.5 m 2 / g, 2 m 2 / g, 1.5 m 2 / g, 1.0 m 2 / g, 0.9 m 2 / g, 0.8 m 2 / g, 0.7 m 2 / g, 0.6 m 2 / g, 0.5 m 2 / g, 0.4 m 2 / g, 0.3 m 2 / g, 0.25 m 2 / g, 0.2 m 2 / g or 0.17 m 2 / g. The BET specific surface area may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0114] The above large-diameter filler may be a hydroxide filler or a non-hydroxide filler, and in one example may be the hydroxide filler described above.

[0115] The lower limit of the weight ratio of the large-diameter filler within the above filler component may be about 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%, or 32 wt%, and the upper limit may be about 50 wt%, 45 wt%, 40 wt%, 35 wt%, 34 wt%, 33 wt%, 32 wt%, 31 wt%, 30 wt%, 28 wt%, or 26 wt%. The weight ratio may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0116] Among the fillers mixed to form the above filler component, the lower limit of the average particle diameter of the filler having the smallest average particle diameter (hereinafter, small-diameter filler) may be about 0.001 μm, 0.001 μm, 0.005 μm, 0.01 μm, 0.05 μm, 0.1 μm, 0.5 μm, 1 μm or 1.5 μm, and the upper limit may be about 10 μm, 9 μm, 8 μm, 7 μm, 6 μm, 5 μm, 4.5 μm, 4 μm, 3.5 μm, 3 μm, 2.5 μm, 2 μm or 1.5 μm. The above average particle diameter is within a range that is equal to or greater than any one of the above-described lower limits; or within a range that is equal to or less than any one of the above-described upper limits; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0117] The lower limit of the BET surface area of ​​the above small-diameter filler is 0.1 m 2 / g, 0.2 m 2 / g, 0.3 m 2 / g, 0.4 m 2 / g, 0.5 m 2 / g, 0.6 m 2 / g, 0.7 m 2 / g, 0.8 m 2 / g, 0.9 m 2 / g, 1 m 2 / g, 1.1 m 2 / g, 1.2 m 2 / g, 1.3 m 2 / g, 1.4 m 2 / g, 1.5 m 2 / g, 1.6 m 2 / g, 1.7 m 2 / g, 1.8 m 2 / g, 1.9 m 2 / g or 2 m 2 / g can be about, and its upper limit is 10 m 2 / g, 9 m 2 / g, 8 m 2 / g, 7 m 2 / g, 6 m 2 / g, 5 m 2 / g, 4.5 m 2 / g, 4 m 2 / g, 3.5 m 2 / g, 3 m 2 / g, 2.5 m 2 / g or 2 m 2 / g. The BET specific surface area may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0118] The lower limit of the weight ratio of the small-diameter filler within the above filler component may be about 30 wt%, 32 wt%, 34 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 44 wt%, 46 wt%, 48 wt% or 50 wt%, and the upper limit may be about 50 wt%, 48 wt%, 46 wt%, 44 wt%, 42 wt%, 40 wt%, 38 wt% or 36 wt%. The weight ratio may be within a range that is more than or exceeds any one of the above-described lower limits; or within a range that is less than or equal to any one of the above-described upper limits; or within a range that is more than or exceeds any one of the above-described lower limits and less than or equal to any one of the above-described upper limits.

[0119] The above small-diameter filler may be a hydroxide filler or a non-hydroxide filler, and in one example may be the non-hydroxide filler described above.

[0120] Within the above filler component, the lower limit of the weight ratio of the small-diameter filler to 100 parts by weight of the large-diameter filler may be 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, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, 160 parts by weight, 180 parts by weight, or 200 parts by weight, and the upper limit may be about 400 parts by weight, 300 parts by weight, 250 parts by weight, 200 parts by weight, 180 parts by weight, 160 parts by weight, 140 parts by weight, 120 parts by weight, or 110 parts by weight. The weight ratio is within a range that is equal to or greater than any one of the lower limits described above; Or within a range that is less than or equal to any one of the upper limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0121] The two or more fillers mixed to form the above filler component may further include, in addition to the large-diameter filler and the small-diameter filler, a filler having an average particle diameter between the large-diameter filler and the small-diameter filler (hereinafter, referred to as a medium-diameter filler). In this case, the lower limit of the average particle diameter of the medium-diameter filler may be about 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm, and the upper limit may be about 45 μm, 40 μm, 35 μm, 30 μm, 25 μm, or 20 μm. The average particle diameter is within a range that is equal to or greater than any one of the lower limits described above; Or within a range that is less than or equal to any one of the upper limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0122] The above medium-diameter filler may have an appropriate level of BET surface area. The lower limit of the BET surface area of ​​the above medium-diameter filler is 0.01 m 2 / g, 0.05 m 2 / g, 0.1 m 2 / g, 0.11 m 2 / g, 0.12 m 2 / g, 0.13 m 2 / g or 0.14 m 2 / g can be about, and its upper limit is 5 m 2 / g, 4.5 m 2 / g, 4 m 2 / g, 3.5 m 2 / g, 3 m 2 / g, 2.5 m 2 / g, 2 m 2 / g, 1.5 m 2 / g, 1.0 m 2 / g, 0.9 m 2 / g, 0.8 m 2 / g, 0.7 m 2 / g, 0.6 m 2 / g, 0.5 m 2 / g, 0.4 m 2 / g, 0.3 m 2 / g, 0.25 m 2 / g, 0.2 m 2 / g, 0.19 m 2 / g, 0.18 m 2 / g, 0.17 m 2 / g, 0.16 m 2 / g, 0.15 m 2 / g or 0.14 m 2 / g. The BET specific surface area may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0123] The lower limit of the weight ratio of the medium-diameter filler within the above filler component may be about 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%, or 32 wt%, and the upper limit may be about 50 wt%, 45 wt%, 40 wt%, 35 wt%, 34 wt%, 33 wt%, 32 wt%, 31 wt%, 30 wt%, 28 wt%, or 26 wt%. The weight ratio may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0124] The above medium-diameter filler, in the above-mentioned formula 3, W S It could be.

[0125] The above medium-diameter filler may be a hydroxide filler or a non-hydroxide filler, and in one example may be the non-hydroxide filler described above.

[0126] For example, the lower limit of the weight ratio of the medium-diameter filler to 100 parts by weight of the large-diameter filler within the filler component may be 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, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, or 100 parts by weight, and the upper limit may be about 300 parts by weight, 250 parts by weight, 200 parts by weight, 180 parts by weight, 160 parts by weight, 140 parts by weight, 120 parts by weight, or 100 parts by weight. The weight ratio may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above, and equal to or less than any one of the upper limits described above.

[0127] The lower limit of the total weight ratio of the large-diameter, medium-diameter, and small-diameter fillers within the filler component may be about 80 wt%, 85 wt%, 90 wt%, 95 wt%, 97 wt%, or 99 wt% based on the total weight of the filler component, and the upper limit may be about 100 wt% based on the total weight of the filler component. The weight ratio may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0128] The above filler component may include at least a low-density filler and a high-density filler. The terms low-density and high-density fillers refer to fillers having a certain level of density. For example, the upper limit of the density of the low-density filler is 3.00 g / cm. 3 , 2.90 g / cm 3 , 2.80 g / cm 3 , 2.70 g / cm 3 , 2.60 g / cm 3 , 2.50 g / cm 3 or 2.45 g / cm 3 It can be of the order of 1.5 g / cm 3 , 2 g / cm 3 , 2.1 g / cm 3 , 2.2 g / cm 3 , 2.3 g / cm 3 or 2.4 g / cm 3 The density of the low-density filler may be within a range that is less than or equal to any one of the upper limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0129] For example, the lower limit of the density of the high-density filler is 3.00 g / cm 3 , 3.1 g / cm 3 , 3.2 g / cm 3 , 3.3 g / cm 3 , 3.4 g / cm 3 , 3.5 g / cm 3 , 3.6 g / cm 3 , 3.7 g / cm 3 , 3.8 g / cm 3 , 3.9 g / cm 3 or 3.95 g / cm 3 It can be of the order of 7 g / cm 3 , 6.5 g / cm 3 , 6 g / cm 3 , 5.5 g / cm 3 , 5 g / cm3 , 4.5 g / cm 3 or 4 g / cm 3 The density of the high-density filler may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0130] The density of the above filler can be measured in a known manner, for example, based on the ASTM D792 standard.

[0131] For example, the lower limit of the weight ratio of the low-density filler in the filler component may be about 30 wt%, 32 wt%, 34 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 44 wt%, 46 wt%, 48 wt%, 50 wt%, 52 wt%, 54 wt%, 56 wt%, 58 wt% or 60 wt%, and the upper limit may be about 90 wt%, 88 wt%, 86 wt%, 84 wt%, 82 wt%, 70 wt%, 78 wt%, 76 wt%, 74 wt%, 72 wt%, 70 wt%, 68 wt%, 66 wt%, 64 wt%, 62 wt%, 60 wt%, 58 wt%, 56 wt%, 54 wt%, It can be about 52 wt%, 50 wt%, 48 wt%, 46 wt%, 44 wt%, 42 wt% or 40 wt%. The weight ratio can be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or less than any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0132] In one example, the low-density filler may be the aforementioned hydroxide filler.

[0133] The curable composition basically contains the above resin component and filler component, and may contain additional components if necessary. The types of components that may be included are not particularly limited.

[0134] For example, one or more of common ingredients such as dispersants, plasticizers, curing catalysts, flame retardants, viscosity modifiers, thixotropic agents, diluents, surface treatment agents, and / or coupling agents may be added as needed.

[0135] The above curable composition can be prepared by mixing each of the components listed above. There are no special restrictions on the mixing method used in this process, and any known mixing method for preparing the composition can be applied.

[0136] In one example, the curable composition may be the main component or the curing agent component of the two-component composition.

[0137] The present specification discloses a two-component composition comprising a subject part and a curing agent part, wherein either or both of the subject part and the curing agent part are the curable composition.

[0138] For example, the subject part may include at least a polyol and a filler component, wherein the polyol may be the aforementioned polyol, and the filler may be the aforementioned filler. In addition, the curing agent part may include at least a polyisocyanate and a filler component, wherein the polyisocyanate may be the aforementioned polyisocyanate.

[0139] The present specification also discloses uses of the curable composition or its cured product. For example, the present application may relate to a product comprising a heat-generating component and a material in contact with the heat-generating component, wherein the material comprises the curable composition or its cured product as described above.

[0140] There are no specific limitations on the type of heat-generating component described above. Any component that generates heat during use or storage and requires heat management can be applied. In the above-described product, a material containing the curable composition or its cured product can be used as a so-called TIM (Thermal Interface Material).

[0141] For example, various electrical and electronic products such as irons, washing machines, dryers, clothes managers, electric shavers, microwave ovens, electric ovens, electric rice cookers, refrigerators, dishwashers, air conditioners, fans, humidifiers, air purifiers, mobile phones, walkie-talkies, televisions, radios, computers or laptops, or battery products such as secondary batteries may contain heat-generating components such as the above.

[0142] For example, in the above product, the material including the curable composition or its cured product may be used to transfer heat generated from the heat-generating component to a cooling portion. In this case, the material may dissipate heat generated from the heat-generating component. The heat-generating component may be a battery cell or a battery module.

[0143] The present specification discloses a curable composition. The curable composition exhibits excellent storage stability without viscosity changes or viscosity unevenness due to sedimentation of the filler, even when containing an excessive amount of filler to achieve high thermal conductivity. The curable composition can simultaneously exhibit both high thermal conductivity and storage stability while using a hydroxide filler as the filler. The present specification also discloses uses of the curable composition.

[0144] Hereinafter, the curable composition and the like will be specifically described through examples and comparative examples, but the scope of the curable composition and the like is not limited by the examples below.

[0145]

[0146] 1. Evaluation of thermal conductivity

[0147] The thermal conductivity of the curable composition was measured using the Hot Disk method according to the ISO 22007-2 standard. Specifically, a mixture of the main part and the curing agent part in a volume ratio of 1:1 of the examples or comparative examples was placed in a mold with a thickness of about 7 mm, cured, and the thermal conductivity was measured in the through-plane direction using the Hot Disk device. As specified in the above standard (ISO 22007-2), the Hot Disk device was a device that can check the thermal conductivity by measuring the temperature change (electrical resistance change) when a sensor having a nickel wire in a double spiral structure is heated. The curing of the curable composition was performed by maintaining a mixture of the main part and the curing agent part in a volume ratio of 1:1 at room temperature (about 25°C) for about 24 hours.

[0148] The mixing of the above-mentioned subject part and hardener part in a volume ratio of 1:1 was performed using equipment (1) connected to two cartridges (2a, 2b, 2) and one static mixer (5) as shown in Fig. 1. For each cartridge (2, 2a, 2b), a cartridge (Sulzer, AB050-01-10-01) was used, which had a circular material injection port with a diameter of 18 mm, a circular material discharge port (4, 4a, 4b) with a diameter of 3 mm, a height of 100 mm, and an internal volume of 25 mL. For the static mixer (5), a stepped static mixer (Sulzer, MBH-06-16T) was used, which had a circular material discharge port (4, 4a, 4b) and a receiving port (6a, 6b) with a diameter of 3 mm, a circular discharge port (7) with a diameter of 2 mm, and 16 elements. The subject and hardener parts loaded into the cartridges (2a, 2b, 2) are pushed at a constant speed of 1 mm / sec by a pressurizing means, TA (Texture analyzer) (3, 3a, 3b), injected into the static mixer (5), mixed, and then the mixture is discharged through the discharge unit (7).

[0149]

[0150] 2. Measurement of average particle size

[0151] The average particle size of the filler referred to herein is the D50 particle size of the filler, which is the particle size measured using a Mastersizer 3000 from Marvern in accordance with the ISO-13320 standard. Ethanol was used as the solvent during the measurement. The incident laser is scattered by the fillers dispersed in the solvent. The intensity and directionality of the scattered laser vary depending on the size of the filler, and the D50 particle size can be obtained by analyzing this using the Mie theory. Through the above analysis, the volume-based cumulative distribution is obtained by converting it into the diameter of a sphere having the same volume as each dispersed filler, and the average particle size (D50 particle size) can be obtained by taking the value at 50% of the cumulative volume as the median value in the distribution.

[0152]

[0153] 3. Evaluation of the sphericity of the filler

[0154] Whether a filler is a spherical filler was evaluated by measuring its sphericity. The sphericity of a filler, which is a three-dimensional particle, is defined as the ratio (S' / S) of the surface area (S) of the particle to the surface area (S') of a sphere having the same volume as the particle, and for actual particles, it is usually the average value of circularity. The circularity is the ratio of the boundary (P) of a two-dimensional image of the particle to the boundary of a circle having the same area (A) as the image, and is theoretically calculated by the following formula. The circularity has a value from 0 to 1, and the circularity is 1 for an ideal circle. In this specification, a filler having a circularity of 0.9 or more is defined as a spherical filler, and a filler having a circularity of less than 0.9, such as an amorphous filler, is defined as a non-spherical filler. This circularity can also be measured using a particle shape analysis device (FPIA-3000) from Marvern.

[0155] <Circularity formula>

[0156] Circularity = 4πA / P 2

[0157]

[0158] 4. Filler density evaluation

[0159] The density of the filler was calculated by calculating the specific gravity of the filler according to the ASTM D792 standard and multiplying the calculated specific gravity by 0.9976.

[0160]

[0161] 5. Evaluation of the specific surface area of ​​the filler

[0162] The BET (Brunauer-Emett-Teller) specific surface area is a specific surface area calculated by the BET (Brunauer-Emett-Teller) method using an adsorption curve obtained by adsorbing nitrogen gas on a sample. The BET specific surface area was obtained by adsorbing nitrogen gas on a filler using an ASAP 2020 (Accelerated Surface Area and Porosimetry System) device.

[0163]

[0164] 6. Density evaluation of the curable composition

[0165] The density of the curable composition was evaluated in the following manner. A mixture of the subject part and the curing agent part of the examples or comparative examples in a volume ratio of 1:1 was injected into a mold, cured to form a cured product of a predetermined volume, and the weight of the cured product was measured. The density of the cured product was then confirmed through the weight and volume. The curing of the curable composition was performed in the same manner as when measuring thermal conductivity.

[0166]

[0167] 7. Evaluation of weight average molecular weight

[0168] The weight-average molecular weight (Mw) was measured using gel permeation chromatography (GPC). In this specification, the unit of weight-average molecular weight is g / mol. The sample to be analyzed was placed in a 20 mL vial and diluted with THF (tetrahydrofuran) to a concentration of approximately 20 mg / mL. The calibration standard sample and the sample to be analyzed were filtered through a syringe filter (pore size: 0.2 μm), and the weight-average molecular weight was measured. Agilent Technologies' ChemStation was used as the analysis program, and the weight-average molecular weight (Mw) was obtained by comparing the elution time with the calibration curve. The measurement conditions for the weight-average molecular weight are as follows.

[0169] <Measurement conditions>

[0170] Device: Agilent Technologies 1200 series

[0171] Column: Using TL Mix. A & B from Agilent Technologies

[0172] Solvent: THF

[0173] Column temperature: 40℃

[0174] Sample concentration: 20 mg / mL, 10 μl injection

[0175] MP: 364000, 91450, 17970, 4910, 1300 used as standard samples

[0176]

[0177] 8. Viscosity measurement

[0178] The viscosity of the curable composition can be measured using a viscometer (Brookfield LV) and a spindle 52Z. The spindle is selected according to the viscosity measurement range. After zeroing the viscometer, the spindle is mounted on the spindle connection, and a plate is mounted on the plate connection. The adjustment lever is adjusted so that a certain gap is created between the spindle and the plate. The plate is separated, and about 0.5 mL of the curable composition is applied to the center of the separated plate, and the plate to which the curable composition has been applied is remounted on the plate connection, and the viscosity is measured for 3 minutes at about 25°C and a rotation speed of 2.4 rpm. The last value after 3 minutes of measurement is taken as the viscosity value of the curable composition.

[0179]

[0180] 9. Storage stability evaluation

[0181] The curable composition (main part or curing agent part) was placed in a 30 mL dispenser syringe (Musach, PSY-30F) (diameter: approximately 26.2 mm, length: approximately 130 mm), and the curable composition was stored for 30 days while maintaining the dispenser syringe in a vertical position. This storage was performed under room temperature (approximately 25°C) and normal pressure (approximately 1 atm) conditions without separately controlling the relative humidity. After the storage, about 0.5 mL of the curable composition was collected from the upper and lower portions of the dispenser syringe. The viscosities of the upper and lower portions were each checked in the manner described in “8. Viscosity Measurement”, and the viscosity deviation was calculated by substituting the upper and lower viscosities into Equation 1 below, and the storage stability and the sedimentation of the filler were determined based on the results.

[0182] [Formula 1]

[0183] △V = 100 × (V L -V U ) / V U

[0184] V in Equation 1 U is the viscosity of the curable composition measured above, and V L is the viscosity of the curable composition measured above.

[0185]

[0186] Example 1

[0187] A two-component curable composition comprising a subject part and a curing agent part was prepared as follows.

[0188] The main part was prepared by mixing a resin component (a1), a filler component (b1), a dispersant (c), and a catalyst (d) in a weight ratio (a1:b1:c:d) of approximately 8.21:91.24:0.46:0.09. The above components were mixed in a rotating stirring vessel at a rotation speed of 600 rpm and a rotation speed of 500 rpm for approximately 3 minutes, and then defoamed again at a rotation speed of 600 rpm and a rotation speed of 200 rpm for approximately 3 minutes to prepare the main part.

[0189] As the above resin component (a1), polyester polyol (Capa TM 2043) (weight average molecular weight: about 400 g / mol) was used. The polyol has an OH value of about 280 mg KOH / g and an acid value of less than about 0.25 mgKOH / g. The OH value is a value measured according to ASTM E 1899-08. The filler component (b1) has an average particle diameter (D50 particle diameter) of about 80 μm and a BET specific surface area of ​​about 0.17 m 2 Filler F1, which is a non-spherical (amorphous) aluminum hydroxide (ATH) of about / g, has an average particle size (D50 particle size) of about 20 μm and a BET specific surface area of ​​about 0.14 m 2 / g of spherical alumina filler F2 and an average particle size (D50 particle size) of about 1.5 μm and a BET specific surface area of ​​about 2.0 m 2 / g of non-spherical alumina filler F3 was mixed in a weight ratio of 25:25:50 (F1:F2:F3).

[0190] DISPERBYK-111 (BYK) was used as the dispersant. In addition, dibutyltin dilaurate was used as the catalyst.

[0191] The hardener part was prepared by mixing the resin component (a2), filler component (b2), dispersant (c), and additive (e) in a weight ratio (a2:b2:c:e) of approximately 8.96:89.55:0.5:1. The above components were mixed in a rotating stirring vessel at a rotation speed of 600 rpm and a rotation speed of 500 rpm for approximately 3 minutes, and then defoamed again at a rotation speed of 600 rpm and a rotation speed of 200 rpm for approximately 3 minutes to prepare the hardener part.

[0192] As the resin component (a2), HDI (Hexamethylene diisocyanate) was used. As the filler component (b2), the filler F1 applied in the main part, the filler F2 applied in the main part, and the average particle diameter (D50 particle diameter) were about 1.5 μm and the BET specific surface area was about 3.5 m 2 / g of non-spherical (amorphous) aluminum hydroxide (ATH) filler F4 was mixed in a weight ratio of 40:40:20 (F1:F2:F4).

[0193] The weighted average particle size of the entire filler component (b2) was approximately 40.3 μm, the weighted average particle size of the hydroxide filler (ATH) was approximately 53.8 μm, the weighted average particle size of the oxide filler (alumina) was approximately 20 μm, the weighted average particle size of the spherical filler was approximately 20 μm, and the weighted average particle size of the non-spherical filler was approximately 53.8 μm.

[0194] The weighted average BET surface area of ​​the entire filler component (b2) is approximately 0.82 m 2 / g, and the weighted average BET surface area of ​​the hydroxide filler was approximately 1.28 m 2 / g, and the weighted average BET surface area of ​​the oxide filler (alumina) was approximately 0.14 m 2 / g, and the weighted average BET surface area of ​​the old filler was about 0.14 m 2 / g, and the weighted average BET surface area of ​​the non-spherical filler was approximately 1.28 m 2 It was around / g.

[0195] DISPERBYK-111 (BYK) was used as the dispersant. In addition, VTMO (vinyl trimethoxy silane) was used as the additive.

[0196]

[0197] Example 2

[0198] The main part was manufactured in the same manner as in Example 1, except that a filler component (b1) applied to the manufacture of the main part was used, in which fillers F1 to F3 of Example 1 were mixed in a weight ratio of 30:30:40 (F1:F2:F3). The same curing agent as in Example 1 was used.

[0199]

[0200] Example 3

[0201] The main part was manufactured in the same manner as in Example 1, except that the filler component (b1) applied to the manufacture of the main part was a filler component obtained by mixing the fillers F1 to F3 of Example 1 in a weight ratio of 32.5:32.5:35 (F1:F2:F3). The same curing agent component as in Example 1 was used.

[0202]

[0203] Comparative Example 1

[0204] The subject part was manufactured in the same manner as in Example 1, except that the filler component (b1) of the subject part was a filler component obtained by mixing the fillers F1 to F3 in a weight ratio of 20:20:60 (F1:F2:F3). The same curing agent as in Example 1 was used.

[0205]

[0206] Comparative Example 2

[0207] As the filler component (b1) applied to the manufacture of the subject part, a filler component was used in which fillers F1 to F3 used in Example 1 were mixed in a weight ratio of 35:35:30 (F1:F2:F3), and the subject part was manufactured in the same manner as in Example 1. The same curing agent part as in Example 1 was used.

[0208]

[0209] Comparative Example 3

[0210] The main part was manufactured in the same manner as in Example 1, except that the filler component (b1) applied to the manufacture of the main part was a filler component obtained by mixing the fillers F1 to F3 of Example 1 in a weight ratio of 40:40:20 (F1:F2:F3). The same curing agent component as in Example 1 was used.

[0211]

[0212] Comparative Example 4

[0213] The main part was manufactured in the same manner as in Example 1, except that the filler component (b1) used in the manufacture of the main part was a filler component obtained by mixing the fillers F1 to F3 of Example 1 in a weight ratio of 40:20:40 (F1:F2:F3). The same curing agent component as in Example 1 was used.

[0214]

[0215] Comparative Example 5

[0216] The filler component (b1) used in the manufacture of the subject part has an average particle diameter (D50 particle diameter) of about 80 μm and a BET specific surface area of ​​about 0.05 m 2 Except that the filler component was used by mixing the spherical alumina filler F5 of about / g with the fillers F2 and F3 of Example 1 in a weight ratio of 25:25:50 (F5:F2:F3).

[0217]

[0218] The weighted average particle diameter and weighted average BET specific surface area of ​​the filler component used in the subject part of the curable composition of the examples and comparative examples are summarized and described in Table 1 below. In Table 1, the average particle diameter is the weighted average particle diameter, and the specific surface area is the weighted average BET specific surface area.

[0219] In Table 1, the unit of particle size is μm, and the unit of BET surface area is m 2 / g is.

[0220] In Table 1, △W1 is the ratio (F / F3) of the weight of the filler with the smallest average particle diameter among the fillers mixed to manufacture the filler component in the subject part and the weights (F) of the remaining fillers, and △W2 is the ratio ((F1 or F5) / F2) of the weight of the filler with the largest average particle diameter among the fillers mixed to manufacture the filler component and the weight (F2) of the filler with the second largest average particle diameter.

[0221] Example Comparative Example 1 2 3 1 2 3 4 5 △ W 1 1 1.5 1.8 6 0.67 2.3 3 4 1.5 1 △ W 2 1 1 1 1 1 1 2 1 Average particle size Total 25.7 5 30.6 3.0 3 20.9 3 5.4 5 40.3 3 6.6 2 5.7 5 ATH 8 0 8 0 8 0 8 0 8 0 - Alumina 7.6 7 9.4 3 10.4 1 6.1 3 11.4 6 13.8 3 7.6 7 2 5.7 5 Spherical 20 20 20 20 20 20 20 50 Non-spherical 27.6 7 35.1 4 39.3 2 1 .1343.7753.8340.751.5Specific surface areaTotal1.080.890.81.260.710.520.91.05ATH0.170.170.170.170.170.170.17-Alumina1.381.201.101.5410.761.381.05Spherical0.140.140.140.140.140.140.140.1Non-spherical1.391.221.121.541.010.781.092

[0222] Regarding the subject part of the curable composition of the examples and comparative examples, △V, V of formula 1 confirmed according to the above “9. Storage stability evaluation” U and V L The thermal conductivity of the cured product of the mixture of the above-mentioned subject part and the hardener part is shown in Table 2 below. In Table 2, △V is the absolute value of the above-mentioned △V. In Table 2, the viscosity V U and V L The unit of is pa·s, the unit of △V is %, and the unit of thermal conductivity is W / m·K.

[0223] Comparative Example 12312345V U 300298290300279265290285V L 300305310300315330305315△V02.356.9012.924.535.1710.53Thermal conductivity33.13.22.83.23.32.93.2

[0224]

[0225] From Table 2, it can be confirmed that the subject part of the example prevents sedimentation of the filler component even when the filler component is included in an excessive amount, thereby ensuring storage stability, and that the cured product exhibits high thermal conductivity.

[0226] In Comparative Examples 1 and 4, although sedimentation of the filler component was prevented to some extent, high thermal conductivity could not be secured, and in Comparative Examples 2, 3 and 5, a large difference occurred in the upper and lower viscosities due to the severe sedimentation of the filler component.

Claims

1. Resin components and Contains filler ingredients, The weight ratio of the above filler component is 70 wt% or more, The above filler component includes a hydroxide filler, It forms a cured product with a thermal conductivity of 3.0 W / m K or higher. A curable composition having an absolute value of △V of the following formula 1 of 10% or less: [Formula 1] △V = 100 × (V L -V U ) / V U V in Equation 1 L and V U are the lower and upper viscosities of the curable composition after maintaining the curable composition at 25°C for 30 days in a vertical dispenser having a capacity of 30 mL and a diameter of 26.2 mm and a length of 130 mm.

2. Resin components and Contains filler ingredients, The weight ratio of the above filler component is 70 wt% or more, The above filler component includes a hydroxide filler, The weighted average BET surface area of ​​the above filler component is 0.75 m 2 / g or more, A curable composition that forms a cured product having a thermal conductivity of 3.0 W / m K or higher.

3. In paragraph 1, the weighted average BET surface area of ​​the filler component is 0.75 m 2 / g or more curable composition.

4. A curable composition according to claim 1 or 2, wherein the weighted average particle size of the filler component is 50 μm or less.

5. A curable composition according to claim 1 or 2, wherein the weighted average particle size of the hydroxide filler is 60 μm or more.

6. A curable composition according to claim 1 or 2, wherein the filler component further comprises a non-hydroxide filler.

7. A curable composition in accordance with claim 6, wherein the weighted average particle size of the non-hydroxide filler is 50 μm or less.

8. A curable composition in accordance with claim 6, wherein the non-hydroxide filler is an oxide filler or a nitride filler.

9. In the first or second paragraph, the weighted average BET surface area of ​​the hydroxide filler is 0.01 to 1 m 2 A curable composition within the range of / g.

10. In paragraph 6, the filler component has a weighted average BET surface area of ​​0.4 m of non-hydroxide filler. 2 / g or more curable composition.

11. A curable composition according to claim 1 or 2, wherein the filler component is a mixture of two or more fillers having different average particle diameters.

12. In the 11th paragraph, a curable composition in which △W1 of the following formula 2 is within a range of 0.5 to 3: [Formula 2] △W1 = W other / IN T W in Equation 2 T is the weight of the filler with the smallest average particle size among the mixed fillers, and W other is the total weight of the filler component, W T It is the value minus .

13. In the 11th paragraph, a curable composition in which △W2 of the following formula 3 is within a range of 0.5 to 2: [Formula 3] △W2 = W F / IN S W in equation 3 F is the weight of the filler with the largest average particle size among the mixed fillers, and W S is the weight of the filler with the second largest average particle size among the fillers being mixed.

14. In clause 12, the average particle diameter of the filler having the smallest average particle diameter among the mixed fillers is within the range of 0.1 μm to 10 μm, and the BET specific surface area is 1 m 2 / g to 10 m 2 A curable composition within the range of / g.

15. In clause 12, the average particle diameter of the filler with the largest average particle diameter among the mixed fillers is 60 μm or more, and the BET specific surface area is 0.1 m 2 / g to 1 m 2 A curable composition within the range of / g.

16. A curable composition in claim 12, wherein the filler having the largest average particle diameter among the mixed fillers is a hydroxide filler.

17. A curable composition according to claim 1 or 2, wherein the resin component is polyol, polyisocyanate or polyurethane.

18. Subject part including subject resin; and Containing a hardener part including a hardener, A two-component composition wherein the subject part or the hardener part is a curable composition according to claim 1 or 2.

19. A heating component; and a material in contact with the heating component, The above material is a product comprising the curable composition of claim 1 or claim 2 or a cured product thereof.

20. A product according to claim 19, wherein the heating component is a battery cell, a battery module or a battery pack.

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