Curable composition

Abstract

This specification discloses curable compositions. These curable compositions exhibit excellent storage stability even when containing fillers to achieve high thermal conductivity, without viscosity changes or inhomogeneities due to excess filler settling, etc. The curable compositions also exhibit both high thermal conductivity and storage stability even when using hydroxide fillers as fillers. This specification discloses the uses of these curable compositions.

Description

Technical Field

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2023-0190434, dated December 22, 2023, the entire disclosure of which is incorporated herein by reference.

[0002] This specification discloses curable compositions and their uses. Background Technology

[0003] In some cases, thermally conductive fillers are formulated into resin components to serve as thermally conductive materials, such as TIM (Thermal Interface Material).

[0004] Generally, the more filler a material contains, the higher its thermal conductivity. Therefore, depending on the application, excess filler is formulated together with the resin components.

[0005] For example, Patent Document 1 discloses the application of a material prepared by formulating a thermally conductive filler in a resin component to a battery, wherein in one example, the material contains a thermally conductive filler in an amount of 85% by weight or greater.

[0006] Typically, fillers have a higher density than resin components, causing them to settle under gravity when stored in materials containing thermally conductive fillers formulated within the resin component. This filler settling leads to changes in material viscosity or viscosity inhomogeneity, which can reduce the processability of the material for application and may result in reduced thermal conductivity and decreased thermal conductivity uniformity, even when it has been used as a thermally conductive material.

[0007] The risk of such problems increases as the filler content in the material increases.

[0008] Among known thermally conductive fillers, hydroxide fillers (such as aluminum hydroxide) possess flame retardancy and a lower density compared to other fillers, making them suitable for applications requiring weight reduction and flame retardancy. However, hydroxide fillers exhibit lower thermal conductivity than other known thermally conductive fillers, necessitating an increase in their content to ensure the desired thermal conductivity when used. This increased content further exacerbates the aforementioned problems.

[0009] [Existing technical documents]

[0010] [Patent Literature]

[0011] (Patent Document 1) Korean Patent Registration No. 10-2393127 Summary of the Invention

[0012] Technical issues

[0013] This specification discloses curable compositions. One object of this specification is to disclose curable compositions that, even when containing excess filler to achieve high thermal conductivity, prevent viscosity changes or viscosity inhomogeneities by preventing filler sedimentation, and ensure storage stability. Another object of this specification is to disclose curable compositions that, even when using hydroxide fillers as fillers, simultaneously ensure high thermal conductivity and storage stability.

[0014] This specification discloses the uses of the curable compositions.

[0015] Technical solution

[0016] Unless otherwise stated, the physical properties mentioned herein that are affected by the measurement temperature are those measured at room temperature.

[0017] The term room temperature refers to the natural temperature without heating or cooling, meaning any temperature in the range of about 10°C to 30°C, such as about 23°C or about 25°C.

[0018] Unless otherwise stated, the unit of temperature in this specification is °C.

[0019] Among the physical properties mentioned in this article, unless otherwise stated, when the measurement pressure affects the results, the relevant physical properties are those measured at normal pressure.

[0020] The term atmospheric pressure refers to natural pressure without pressurization or depressurization, which typically refers to pressure in the range of approximately 700 mmHg to 800 mmHg.

[0021] Unless otherwise stated, the physical properties mentioned in this article that affect the measurement results of humidity are those measured under standard humidity conditions.

[0022] Standard humidity means relative humidity (RH%) in the range of about 50% to 60%, and for example, means relative humidity (RH%) of about 50%, 55% or 60%.

[0023] In this specification, unless otherwise stated, the average particle size of the filler refers to the so-called D50 particle size (median diameter). The method for measuring the D50 particle size is summarized in "2. Measurement of Average Particle Size" of the Examples section of this specification.

[0024] In this specification, the terms spherical packing and non-spherical packing are distinguished by their roundness, and the categories of non-spherical packing may include rectangular packing, amorphous packing, disc packing, or needle packing, etc.

[0025] In this specification, packing material with a roundness of about 0.9 or greater, or 0.95 or greater, can be designated as spherical packing material, while packing material with a roundness of less than 0.95, or less than 0.9, can be designated as non-spherical packing material. Sphericity can be determined through particle shape analysis of the packing material. The sphericity of a packing material that is a three-dimensional particle is defined as the ratio (S' / S) of the surface area (S) of the packing material to the surface area (S') of a sphere having the same volume as the packing material. For actual packing materials, roundness is typically used. Roundness is expressed as the ratio of the boundary (P) of a two-dimensional image obtained from the actual packing material to the boundary of a circle having the same area (A) as the area of ​​the same image, obtained using the following formula:

[0026] <Circularity>

[0027] Circularity = 4πA / P 2

[0028] Circularity is expressed as a value from 0 to 1, where a perfect circle has a value of 1, and the more irregular the shape, the less than 1 the circularity value. In this specification, sphericity values ​​are the average of the circularity measured using a Malvern Particle Shape Analyzer (FPIA-3000).

[0029] This specification discloses curable compositions. The term curable composition means a composition that can be cured. The term curing means the phenomenon in which the viscosity and / or hardness of the composition increases due to chemical and / or physical reactions or interactions.

[0030] Curable compositions can be solvent-based or solvent-free. The term "solvent-based composition" means a composition containing a solvent (aqueous or organic), and the term "solvent-free composition" means a composition substantially free of solvent. In solvent-free compositions, the upper limit of solvent content can be approximately 5% by weight, 4% by weight, 3% by weight, 2% by weight, 1% by weight, 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight, 0.005% by weight, 0.001% by weight, 0.0005% by weight, or 0.0001% by weight, and the lower limit can be approximately 0% by weight. The solvent content in a solvent-free composition can be less than or equal to, or less than, any of the above upper limits; or greater than or equal to, or greater than the above lower limit while simultaneously less than or equal to, or less than any of the above upper limits.

[0031] The curable composition can be an energy-curing (e.g., ultraviolet) curable composition, a moisture-curing composition, a thermosetting composition, or a room-temperature curing composition. When the curable composition is an energy-curing type, curing of the curable composition can be carried out by irradiating the composition with energy rays such as ultraviolet light; when the curable composition is a moisture-curing type, curing of the curable composition can be carried out by keeping the composition under appropriate moisture; when it is a thermosetting type, curing of the curable composition can be carried out by applying appropriate heat to the composition; or when it is a room-temperature curing type, curing of the curable composition can be carried out by keeping the composition at room temperature.

[0032] In one instance, the curable composition can be a room temperature curing composition, and in particular, a composition in which curing is achieved by holding the composition at room temperature without applying external energy such as energy rays or excessive moisture.

[0033] The curable composition can be a one-component composition or a two-component composition, and in some cases, it can be any part of a two-component composition.

[0034] The term "one-component composition" means a composition in which all components necessary for curing are present in a known mixed state, and which cures if certain conditions are met (e.g., application of heat or energy rays, exposure to moisture, etc.).

[0035] The term two-component composition means a composition in which the components required for curing are present in a physically separate state (e.g., as a main component and a curing agent component), and the separate components are mixed and cured by exposure to a curable environment as is known.

[0036] The curable compositions exhibit excellent storage stability even when containing excess filler, as described below.

[0037] Excellent storage stability can be reflected by ΔV as shown in Equation 1.

[0038] [Formula 1]

[0039] ΔV = 100 × (V L -V U ) / V U

[0040] In Equation 1, V L and V UThe lower and upper viscosities of the curable composition were determined by introducing the curable composition into a 30 mL dispenser syringe with a diameter of 26.2 mm and a length of 130 mm, then holding the dispenser syringe vertically and maintaining it at 25°C for 30 days.

[0041] The method for obtaining ΔV in Equation 1 is described in detail in "9. Storage Stability Assessment" of the Embodiments section of this specification.

[0042] The smaller the absolute value of ΔV in Equation 1, the more likely it is that the packing material will not settle while maintaining a uniform mixing state under vertical storage conditions.

[0043] The lower limit of the absolute value of ΔV in Equation 1 can be approximately 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, or 6.5%, and its upper limit can be approximately 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or 0.5%. The absolute value of ΔV can be less than or equal to, or less than any of the above upper limits; or it can be greater than or equal to, or greater than any of the above lower limits while being less than or equal to, or less than any of the above upper limits.

[0044] In Equation 1, ΔV can be positive or negative. Generally, if the above vertical orientation is maintained, the lower viscosity (Vc) of the composition can be cured. L The viscosity may be greater than that of the upper part (V). U This means that ΔV can usually be a positive number, but it can also be a negative number.

[0045] Curable compositions exhibit excellent storage stability even when they contain excess filler to ensure high thermal conductivity. For example, the lower limit of the thermal conductivity of a curable composition or a cured product of a curable composition may be around 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 around 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. Thermal conductivity can be greater than or equal to, or greater than any of the lower limits mentioned above; or it can be greater than or equal to, or greater than any of the lower limits mentioned above while being less than or equal to, or less than any of the upper limits mentioned above. Thermal conductivity can be evaluated in accordance with the method described in "1. Evaluation of Thermal Conductivity" of the Embodiments section of this specification.

[0046] Curable compositions may contain at least a resin component and a filler component.

[0047] There are no particular limitations on the type of resin component. For example, a wide variety of known components used in the formation of thermally conductive materials (such as so-called thermal interface materials (TIMs)) can be used as resin components.

[0048] Examples of such components include polyurethane components, silicone components, epoxy resin components, or acrylic resin components.

[0049] In one instance, the resin component may be a polyurethane component. The term polyurethane component includes known polyurethanes (polymer compounds bonded by urethane bonds) or components capable of forming polyurethanes through chemical and / or physical reactions.

[0050] Polyols and polyisocyanates are known components capable of forming polyurethanes. These components can be reacted with urethanes to form polyurethanes. In some cases, chain extenders can also react with polyols and / or polyisocyanates to form polyurethanes. When the curable composition is the main component or curing agent component of a two-component composition, the curable composition may contain a portion of a polyol, a polyisocyanate, and a chain extender as an optional component.

[0051] In this specification, the term polyol means a compound containing two or more hydroxyl groups. For example, a compound having two hydroxyl groups is generally called a diol, and a compound having three hydroxyl groups is called a triol, wherein these diols and triols are also types of polyols.

[0052] The lower limit for the number of hydroxyl groups in a polyol can be 2 or 3, and the upper limit can be 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of hydroxyl groups can be less than or equal to, or less than any of the above upper limits; or greater than or equal to, or greater than any of the above lower limits; or greater than or equal to, or greater than any of the above lower limits while simultaneously less than or equal to, or less than any of the above upper limits.

[0053] Polyols can have hydroxyl values ​​(OH values) within an appropriate range. The hydroxyl value of a polyol can be measured according to ASTM E1899-08 standard. The lower limit of the hydroxyl value can be approximately 100 mgKOH / g, 150 mgKOH / g, 200 mgKOH / g, or 250 mgKOH / g, and the upper limit can be approximately 500 mgKOH / g, 450 mgKOH / g, 400 mgKOH / g, 350 mgKOH / g, or 300 mgKOH / g. The hydroxyl value can be greater than or equal to, or greater than, any of the lower limits mentioned above; or less than or equal to, or less than, any of the upper limits mentioned above; or less than or equal to, or less than, any of the upper limits mentioned above while simultaneously greater than or equal to, or greater than, any of the lower limits mentioned above.

[0054] Polyols can have acid values ​​within a suitable range. Methods for measuring the acid value of polyols are described in the Examples section of this specification. The lower limit of the acid value can be approximately 0 mg KOH / g, and its upper limit can be approximately 5 mg KOH / g, 4 mg KOH / g, 3 mg KOH / g, 2 mg KOH / g, 1 mg KOH / g, 0.9 mg KOH / g, 0.8 mg KOH / g, 0.7 mg KOH / g, 0.6 mg KOH / g, 0.5 mg KOH / g, 0.4 mg KOH / g, or 0.3 mg KOH / g. The acid value can be greater than or equal to, or greater than, any of the lower limits mentioned above; or less than or equal to, or less than, any of the upper limits mentioned above; or both less than or equal to, or less than, any of the upper limits mentioned above and greater than or equal to, or greater than, any of the lower limits mentioned above.

[0055] The lower limit of the molecular weight or weight-average molecular weight of polyols can be approximately 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 can be approximately 1,000 g / mol, 900 g / mol, 800 g / mol, 700 g / mol, 600 g / mol, or 500 g / mol. This molecular weight or weight-average molecular weight can be greater than or equal to, or greater than, any of the lower limits mentioned above; or less than or equal to, or less than, any of the upper limits mentioned above; or both less than or equal to, or less than the upper limits mentioned above and greater than or equal to, or greater than any of the lower limits mentioned above.

[0056] As a polyol, any known polyol can be used without particular limitation. Polyether polyols or polyester polyols are known as polyols for forming polyurethanes, and such polyols can be used in curable compositions.

[0057] Polyether polyols commonly known include (poly)ethylene glycol, diethylene glycol, (poly)propylene glycol, 1,2-butanediol, 2,3-butanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,2-ethylhexanediol, 1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol, 1,3-cyclohexanediol and 1,4-cyclohexanediol, (poly)ethylene glycerol, diethylene glycol, (poly)propylene glycerol, glycerol, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,3,4-hexanetriol, 1,3,6-hexanetriol units and / or trimethylolpropane, etc.

[0058] In one instance, polyester polyols can be used as polyols. So-called carboxylic acid-based polyols and caprolactone-based polyols are known as polyester polyols, and such polyols can be used alone or in combination of both or more as resin components.

[0059] For example, polyester polyols can be polyols represented by the following chemical formula 1 or chemical formula 2:

[0060] [Chemical Formula 1]

[0061]

[0062] [Chemical Formula 2]

[0063]

[0064] In Formula 1 and Formula 2, X is a dicarboxylic acid derivative unit, Y is a polyol derivative unit (e.g., a triol unit or a diol unit), and n and m are arbitrary numbers.

[0065] The dicarboxylic acid derivative unit is a unit formed by reacting a dicarboxylic acid with a polyol as a carbamate, and the polyol derivative unit is a unit formed by reacting a polyol with a dicarboxylic acid or caprolactone as a carbamate.

[0066] That is, when the hydroxyl group of a polyol reacts with the carboxyl group of a dicarboxylic acid, water (H2O) molecules are released through a condensation reaction, and an ester bond is formed at the same time. In the above chemical formula 1, X refers to the part that excludes the ester bond after the dicarboxylic acid forms an ester bond through a condensation reaction, and Y also refers to the part that excludes the ester bond after the polyol forms an ester bond through a condensation reaction. The ester bond is represented in chemical formula 1.

[0067] The Y in chemical formula 2 also represents the portion of the ester bond that is excluded after the polyol forms an ester bond with caprolactone.

[0068] In chemical formulas 1 and 2, when the polyol derivatizing unit Y is derived from a unit of a polyol containing three or more hydroxyl groups, such as a triol unit, a structure in which Y is partially branched in the structure of the above chemical formulas can be realized.

[0069] There is no particular limitation on the type of dicarboxylic acid derivative unit X in Formula 1. For example, the unit may be selected from any one, or two or more, units selected from the following: phthalic acid unit, isophthalic acid unit, terephthalic acid unit, trimellitic acid unit, tetrahydrophthalic acid unit, hexahydrophthalic acid unit, tetrachlorophthalic acid unit, oxalic acid unit, adipic acid unit, azelaic acid unit, sebacic acid unit, succinic acid unit, malic acid unit, glutaric acid unit, malonic acid unit, pimelic acid unit, octanoic acid unit, 2,2-dimethylsuccinic acid unit, 3,3-dimethylglutaric acid unit, 2,2-dimethylglutaric acid unit, maleic acid unit, fumaric acid unit, itaconic acid unit, and fatty acid unit.

[0070] In Formulas 1 and 2, there is no particular limitation on the type of polyol-derived unit Y. For example, the unit can be any one or two or more units selected from the following: ethylene glycol unit, propylene glycol unit, 1,2-butanediol unit, 2,3-butanediol unit, 1,3-propanediol unit, 1,3-butanediol unit, 1,4-butanediol unit, 1,6-hexanediol unit, neopentyl glycol unit, 1,2-ethylhexanediol unit, 1,5-pentanediol unit, 1,10-decanediol unit, 1,3-cyclohexanediethanol unit, 1,4-cyclohexanediethanol unit, glycerol unit, and trimethylolpropane unit.

[0071] In chemical formula 1, n and m are arbitrary numbers, and their ranges can be chosen with consideration of desired physical properties.

[0072] For example, the lower limit of n can be around 2 or 3, and its upper limit can be around 10, 9, 8, 7, 6, or 5. n can be less than or equal to, or less than any of the upper limits mentioned above; or greater than or equal to, or greater than any of the lower limits mentioned above; or greater than or equal to, or greater than any of the lower limits mentioned above while simultaneously less than or equal to, or less than any of the upper limits mentioned above.

[0073] For example, the lower limit of m can be around 2 or 3, and its upper limit can be around 10, 9, 8, 7, 6, or 5. m can be less than or equal to, or less than any of the above upper limits; or greater than or equal to, or greater than any of the above lower limits; or greater than or equal to, or greater than any of the above lower limits while simultaneously less than or equal to, or less than any of the above upper limits.

[0074] Polyisocyanates can also be used as resin components. The term polyisocyanate can refer to a compound having two or more isocyanate groups. The lower limit of the number of isocyanate groups in a polyisocyanate can be around 2 or 3, and the upper limit can be around 10, 9, 8, 7, 6, 5, 4, 3, or 2. The number of isocyanate groups can be greater than or equal to, or greater than any of the lower limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above while being greater than or equal to, or greater than any of the lower limits mentioned above.

[0075] As polyisocyanates, those commonly used in the industry (e.g., those commonly used to form polyurethanes) can be used without particular limitation. Although there is no particular limitation, for example, as polyisocyanates, diisocyanates (compounds having two isocyanate groups) and / or polyisocyanates having three or more isocyanate groups can be used.

[0076] When the curable composition is the main component or curing agent component of the above two-component composition, the resin component may contain at least one selected from polyols and polyisocyanates.

[0077] The content of the resin component in the curable composition can be determined based on the filler component contained in the resin component. For example, the lower limit of the weight ratio of the resin component relative to 100 parts by weight of the filler component in the curable composition can be approximately 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 can be approximately 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. This weight ratio can be greater than or equal to, or greater than any of the lower limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above while simultaneously greater than or equal to, or greater than any of the lower limits mentioned above.

[0078] When both polyols and polyisocyanates are included as resin components, there is no restriction on the ratio between the two components, and, for example, this ratio can be controlled so that the two components can react to form polyurethane. In one example, when both components are included, the ratio (OH / NCO) of the molar number of hydroxyl groups (OH) in the polyol to the molar number of isocyanate groups (NCO) in the polyisocyanate can be considered to adjust the ratio between them. For example, the lower limit of the OH / NCO ratio can be around 0.01, 0.05, 0.1, 0.5, or 1, and its upper limit can be around 100, 50, 25, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1. The OH / NCO ratio can be greater than or equal to, or greater than any of the lower limits mentioned above; less than or equal to, or less than any of the upper limits mentioned above; or both less than or equal to, or less than the upper limits mentioned above and greater than or equal to, or greater than any of the lower limits mentioned above.

[0079] In one example, when the curable composition is a main component or a curing agent component of a two-component composition, the main component may contain a polyol in the curable compound, and the curing agent component may contain a polyisocyanate in the curable compound.

[0080] Curable compositions include filler components along with resin components. The term filler component refers to a component consisting solely of fillers. Thus, for example, all fillers contained in a curable composition can be combined to form a filler component.

[0081] In the curable composition, the lower limit of the weight percentage of the filler component can be approximately 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 can be approximately 99 wt%, 98 wt%, 97 wt%, 96 wt%, 95 wt%, 94 wt%, 93 wt%, or 92 wt%. The weight percentage of the filler component can be greater than or equal to, or greater than any of the aforementioned lower limits; or it can be less than or equal to, or less than any of the aforementioned upper limits while simultaneously being greater than or equal to, or greater than any of the aforementioned lower limits.

[0082] In curable compositions, in order to ensure desired properties such as thermal conductivity, excellent storage stability as described above can be ensured even when containing excess filler components as mentioned above.

[0083] The filler component may include a thermally conductive filler, or may be a thermally conductive filler component. The terms thermally conductive filler or thermally conductive filler component refer to a filler or filler component that enables the curable composition or the cured product of the curable composition to exhibit the aforementioned thermal conductivity through the relevant filler or filler component.

[0084] Examples of fillers capable of forming filler components include 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; metallic fillers, such as copper, silver, iron, aluminum, or nickel; metallic alloy fillers, such as titanium; or silicon powder, such as quartz, glass, or silicon dioxide; and so on, but are not limited to these. Furthermore, carbon fillers, such as graphite or activated carbon, may also be considered to ensure insulating properties.

[0085] The packing composition may contain one, two or more types of packing.

[0086] The filler may contain at least the hydroxide filler described above. Hydroxide fillers have excellent insulation or flame retardancy and a lower density compared to other fillers, which is beneficial for forming lighter materials. However, even when using such hydroxide fillers, the desired high thermal conductivity and storage stability can be ensured simultaneously.

[0087] The lower limit of the hydroxide filler content in the filler component can be approximately 20% by weight, 22% by weight, 24% by weight, 26% by weight, 28% by weight, 30% by weight, or 32% by weight, and the upper limit can be, for example, approximately 50% by weight, 45% by weight, 40% by weight, 35% by weight, 34% by weight, 33% by weight, 32% by weight, 31% by weight, 30% by weight, or 28% by weight. This weight ratio can be greater than or equal to, or greater than any of the aforementioned lower limits; or less than or equal to, or less than any of the aforementioned upper limits; or less than or equal to, or less than any of the aforementioned upper limits while simultaneously being greater than or equal to, or greater than any of the aforementioned lower limits.

[0088] To ensure storage stability, flame retardancy, and thermal conductivity, the filler composition can be adjusted.

[0089] For example, the weighted average BET specific surface area of ​​the packing components can be adjusted. The weighted average BET specific surface area is the weighted average obtained by calculating the BET specific surface area of ​​all mixed packings considering the mixing weight ratio when a packing component is formed by mixing multiple packings. For example, when a packing component is formed by mixing packing (1) with a BET specific surface area of ​​B1 and packing (2) with a BET specific surface area of ​​B2 in a weight ratio of W1:W2 (1:2), the weighted average BET specific surface area is the value obtained according to (B1×W1+B2×W2) / (W1+W2). The method for obtaining the BET specific surface area of ​​each packing is described in "5. Evaluation of Packing Specific Surface Area" of the Examples section of this specification.

[0090] The smaller the BET specific surface area of ​​the filler component, the lower the degree of interaction between the filler component and another component, such as the resin component; and conversely, the higher the BET specific surface area of ​​the filler component, the higher the degree of interaction between the filler component and another component, such as the resin component, and therefore, the purpose can be to adjust the BET specific surface area to an appropriate level.

[0091] The lower limit of the weighted average BET specific surface area of ​​the filler components can be 0.75 m². 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 Approximately / g, with an upper limit of 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 The weighted average BET surface area can be greater than or equal to, or greater than any of the lower limits mentioned above; or it can be less than or equal to, or less than any of the upper limits mentioned above while being greater than or equal to, or greater than any of the lower limits mentioned above.

[0092] The weighted average BET specific surface area of ​​the hydroxide packing component can also be adjusted. Here, the meaning of the weighted average BET specific surface area is as described above. The lower limit of the weighted average BET specific surface area of ​​the hydroxide packing can be 0.01 m². 2 / g, 0.05 m 2 / g, 0.10 m 2 / g or 0.15 m 2 Approximately / g, with an upper limit of 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, 0.5m 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 2The weighted average BET surface area can be greater than or equal to, or greater than any of the lower limits mentioned above; less than or equal to, or less than any of the upper limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above while being greater than or equal to, or greater than any of the lower limits mentioned above.

[0093] In addition to hydroxide fillers, the packing composition may also contain non-hydroxide fillers. In this case, non-hydroxide fillers mean any filler present in the packing composition other than hydroxide fillers, and specific examples include, but are not limited to, oxide fillers, nitride fillers, carbide fillers, metal fillers, metal alloy fillers, silicon powder and / or carbon fillers as described above.

[0094] The weighted average BET specific surface area of ​​the non-hydroxide packing components can also be adjusted. Here, the meaning of the weighted average BET specific surface area is as described above. The lower limit of the weighted average BET specific surface area of ​​the non-hydroxide packing can be 0.4 m². 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 Approximately / g, with an upper limit of 10m. 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 The weighted average BET surface area can be greater than or equal to, or greater than any of the lower limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above while being greater than or equal to, or greater than any of the lower limits mentioned above.

[0095] The weighted average particle size of the filler components can be adjusted. The weighted average particle size is the average value obtained by calculating the average particle size of all mixed fillers considering the mixing weight ratio when the filler components are formed by mixing multiple fillers. For example, when filler (1) with an average particle size of D1 and filler (2) with an average particle size of D2 are mixed at a weight ratio of W1:W2 (1:2), the weighted average particle size is the value obtained according to (D1×W1+D2×W2) / (W1+W2).

[0096] The lower limit of the weighted average particle size of the filler component can be approximately 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm, and the upper limit can be approximately 50 μm, 45 μm, 40 μm, 35 μm, or 30 μm. The weighted average particle size of the filler component can be less than or equal to, or less than any of the above upper limits; or it can be less than or equal to, or less than any of the above upper limits while being greater than or equal to, or greater than any of the above lower limits.

[0097] The weighted average particle size of the hydroxide filler contained in the filler component can be adjusted. The meaning of weighted average particle size is as described above. The lower limit of the weighted average particle size of the hydroxide filler can be approximately 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, or 80 μm, and its upper limit can be approximately 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 can be greater than or equal to, or greater than any of the above lower limits; or it can be less than or equal to, or less than any of the above upper limits while being greater than or equal to, or greater than any of the above lower limits.

[0098] The weighted average particle size of the non-hydroxide filler in the filler component can be adjusted. The meaning of weighted average particle size is as described above. The lower limit of the weighted average particle size of the non-hydroxide filler can be approximately 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm, and its upper limit can be approximately 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. This weighted average particle size can be less than or equal to, or less than any of the above upper limits; or it can be less than or equal to, or less than any of the above upper limits while being greater than or equal to, or greater than any of the above lower limits.

[0099] The weighted average particle size of the non-spherical packing material in the packing component can also be adjusted. The meaning of weighted average particle size is as described above. The lower limit of the weighted average particle size of the non-spherical packing material can be approximately 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, or 35 μm, and its upper limit can be approximately 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 above weighted packing particle size can be less than or equal to, or less than any of the above upper limits; or it can be less than or equal to, or less than any of the above upper limits while being greater than or equal to, or greater than any of the above lower limits.

[0100] The packing component may contain a certain range of non-spherical packings. The lower limit of the content of non-spherical packings in the packing component may be approximately 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, or 75% by weight, and the upper limit may be approximately 90%, 85%, 80%, 75%, or 70% by weight. This weight ratio may be greater than or equal to, or greater than, any of the aforementioned lower limits; or less than or equal to, or less than, any of the aforementioned upper limits; or less than or equal to, or less than, any of the aforementioned upper limits while simultaneously greater than or equal to, or greater than, any of the aforementioned lower limits.

[0101] The weighted average particle size of the spherical packing material contained in the packing component can be adjusted. The meaning of weighted average particle size is as described above. The lower limit of the weighted average particle size can be approximately 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, or 20 μm, and its upper limit can be approximately 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, 30 μm, or 20 μm. The weighted packing particle size can be greater than or equal to, or greater than any of the above lower limits; or less than or equal to, or less than any of the above upper limits; or less than or equal to, or less than any of the above upper limits while simultaneously greater than or equal to, or greater than any of the above lower limits.

[0102] The filler composition can be prepared, for example, by mixing two or more fillers with different average particle sizes. In this case, the upper limit of the quantity of the mixed filler can be approximately 10, 9, 8, 7, 6, 5, 4, or 3, and the lower limit can be 2. The type of filler can be greater than or equal to, or greater than any of the above lower limits; or it can be less than or equal to, or less than any of the above upper limits while being greater than or equal to, or greater than any of the above lower limits.

[0103] In this case, ΔW1 of the filler component according to formula 2 can be adjusted.

[0104] [Equation 2]

[0105] ΔW1=W 其他 / W T

[0106] In Equation 2, W T The weight of the packing material with the smallest average particle size in the mixed packing, and W 其他 To subtract the weight W from the total weight of the filler components T The value obtained.

[0107] The lower limit of ΔW1 can be approximately 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 its upper limit can be approximately 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 ΔW1 can be greater than or equal to, or greater than any of the aforementioned lower limits; or less than or equal to, or less than any of the aforementioned upper limits; or less than or equal to, or less than any of the aforementioned upper limits while simultaneously being greater than or equal to, or greater than any of the aforementioned lower limits.

[0108] By distributing the packing material so that ΔW1 falls within the above range, both the desired high thermal conductivity and storage stability can be ensured simultaneously. If ΔW1 is too small, thermal conductivity may not be effectively ensured, while if ΔW1 is too large, a deviation between the upper and lower viscosity may occur due to the settling of the packing components.

[0109] In this case, ΔW2 of Equation 3 for the filler component can fall within a certain range.

[0110] [Formula 3]

[0111] ΔW2=W F / W S

[0112] In Equation 3, W F The weight of the packing material with the largest average particle size in the mixed packing, and W S This is the weight of the packing material with the second largest average particle size in the mixed packing.

[0113] In Equation 3 above, the lower limit of ΔW2 can be approximately 0.1, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0, and its upper limit can be approximately 2, 1.5, 1.4, 1.3, 1.2, 1.1, or 1.0. The value of ΔW2 can be greater than or equal to, or greater than any of the aforementioned lower limits; less than or equal to, or less than any of the aforementioned upper limits; or less than, or equal to, or less than any of the aforementioned upper limits while simultaneously being greater than or equal to, or greater than any of the aforementioned lower limits.

[0114] For the formation of the packing components, the average particle size of the packing with the largest average particle size in the mixed packing (hereinafter referred to as large-diameter packing) can be adjusted. For example, the lower limit of the average particle size of the large-diameter packing can be approximately 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, or 80 μm, and its upper limit can be approximately 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. This average particle size can be greater than or equal to, or greater than any of the above lower limits; or it can be less than or equal to, or less than any of the above upper limits while being greater than or equal to, or greater than any of the above lower limits.

[0115] The lower limit of the BET specific surface area for large-diameter packing can be 0.01 m². 2 / g, 0.05 m 2 / g, 0.1 m 2 / g, 0.15m2 / g or 0.17 m 2 Approximately / g, with an upper limit of 5 m 2 / g, 4.5 m 2 / g、4 m 2 / g, 3.5 m 2 / g、3 m 2 / g, 2.5m 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, 0.4m 2 / g, 0.3 m 2 / g, 0.25 m 2 / g, 0.2 m 2 / g or 0.17 m 2 The specific surface area of ​​BET can be greater than or equal to, or greater than any of the lower limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above while being greater than or equal to, or greater than any of the lower limits mentioned above.

[0116] Large-diameter packing can be hydroxide packing or non-hydroxide packing, and in one instance, it can be hydroxide packing as described above.

[0117] The lower limit of the weight ratio of large-diameter packing in the packing component can be approximately 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%, or 32 wt%, and the upper limit can be approximately 50 wt%, 45 wt%, 40 wt%, 35 wt%, 34 wt%, 33 wt%, 32 wt%, 31 wt%, 30 wt%, 28 wt%, or 26 wt%. This weight ratio can be greater than or equal to, or greater than any of the above lower limits; or less than or equal to, or less than any of the above upper limits; or less than or equal to, or less than any of the above upper limits while simultaneously greater than or equal to, or greater than any of the above lower limits.

[0118] For the formation of the packing components, the lower limit of the average particle size of the packing with the smallest average particle size in the mixed packing (hereinafter, small diameter packing) can be approximately 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 its upper limit can be approximately 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. This average particle size can be greater than or equal to, or greater than any of the aforementioned lower limits; or less than or equal to, or less than any of the aforementioned upper limits; or less than or equal to, or less than any of the aforementioned upper limits while simultaneously being greater than or equal to, or greater than any of the aforementioned lower limits.

[0119] The lower limit of the BET specific surface area for small-diameter packings can be 0.1 m². 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 Approximately / g, with an upper limit of 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 m2 The specific surface area of ​​BET can be greater than or equal to, or greater than any of the lower limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above while being greater than or equal to, or greater than any of the lower limits mentioned above.

[0120] The lower limit of the weight ratio of small-diameter packing within the packing component can be approximately 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, or 50% by weight, and the upper limit can be approximately 50%, 48%, 46%, 44%, 42%, 40%, 38%, or 36% by weight. This weight ratio can be greater than or equal to, or greater than any of the aforementioned lower limits; or less than or equal to, or less than any of the aforementioned upper limits; or less than or equal to, or less than any of the aforementioned upper limits while simultaneously being greater than or equal to, or greater than any of the aforementioned lower limits.

[0121] Small-diameter packing can be hydroxide packing or non-hydroxide packing, and in one instance, it can be non-hydroxide packing as described above.

[0122] In the packing composition, the lower limit of the weight ratio of small-diameter packing relative to 100 parts by weight of large-diameter packing can be approximately 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, or 200 parts by weight, and the upper limit can be approximately 400, 300, 250, 200, 180, 160, 140, 120, or 110 parts by weight. This weight ratio can be greater than or equal to, or greater than any of the above lower limits; or less than or equal to, or less than any of the above upper limits; or less than or equal to, or less than any of the above upper limits while simultaneously greater than or equal to, or greater than any of the above lower limits.

[0123] In addition to large-diameter and small-diameter packings, the mixed packings used to form the packing composition may also include packings whose average particle size falls between that of large-diameter and small-diameter packings (hereinafter referred to as medium-diameter packings). In this case, the lower limit of the average particle size of the medium-diameter packing may be approximately 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm, and its upper limit may be approximately 45 μm, 40 μm, 35 μm, 30 μm, 25 μm, or 20 μm. This average particle size may be greater than or equal to, or greater than any of the lower limits mentioned above; less than or equal to, or less than any of the upper limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above while simultaneously being greater than or equal to, or greater than any of the lower limits mentioned above.

[0124] Medium-diameter packings can possess an appropriate level of BET specific surface area. The lower limit of the BET specific surface area for medium-diameter packings can be 0.01 m². 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 Approximately / g, with an upper limit of 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, 1.5m 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 The specific surface area of ​​BET can be greater than or equal to, or greater than any of the lower limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above while being greater than or equal to, or greater than any of the lower limits mentioned above.

[0125] The lower limit of the weight ratio of medium-diameter packing in the packing component can be approximately 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%, or 32 wt%, and the upper limit can be approximately 50 wt%, 45 wt%, 40 wt%, 35 wt%, 34 wt%, 33 wt%, 32 wt%, 31 wt%, 30 wt%, 28 wt%, or 26 wt%. This weight ratio can be greater than or equal to, or greater than any of the above lower limits; or less than or equal to, or less than any of the above upper limits; or less than or equal to, or less than any of the above upper limits while simultaneously greater than or equal to, or greater than any of the above lower limits.

[0126] Medium diameter packing can be W in formula 3 above. S .

[0127] The medium-diameter packing can be hydroxide packing or non-hydroxide packing, and in one example, it can be non-hydroxide packing as described above.

[0128] For example, within the packing composition, the lower limit of the weight ratio of medium-diameter packing relative to 100 parts by weight of large-diameter packing can be approximately 10, 20, 30, 40, 50, 60, 60, 70, 80, 90, or 100 parts by weight, and the upper limit can be approximately 300, 250, 200, 180, 160, 140, 120, or 100 parts by weight. This weight ratio can be greater than or equal to, or greater than any of the aforementioned lower limits; or less than or equal to, or less than any of the aforementioned upper limits; or less than or equal to, or less than any of the aforementioned upper limits while simultaneously being greater than or equal to, or greater than any of the aforementioned lower limits.

[0129] Based on the total weight of the packing components, the lower limit of the total weight ratio of large-diameter, medium-diameter, and small-diameter packing within the packing components can be approximately 80% by weight, 85% by weight, 90% by weight, 95% by weight, 97% by weight, or 99% by weight, and the upper limit based on the total weight of the packing components can be approximately 100% by weight. This weight ratio can be greater than or equal to, or greater than any of the aforementioned lower limits; or less than or equal to, or less than any of the aforementioned upper limits; or less than or equal to, or less than any of the aforementioned upper limits while simultaneously being greater than or equal to, or greater than any of the aforementioned lower limits.

[0130] The packing composition may include at least low-density packing and high-density packing. The terms low-density packing and high-density packing refer to packing with a certain level of density. For example, the upper limit of the density of low-density packing can be 3.00 g / cm³. 3 2.90g / 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 The upper and lower limits are approximately 1.5 g / cm³. 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 low-density fillers can be less than or equal to, or less than any of the above upper limits; or it can be less than or equal to, or less than any of the above upper limits while being greater than or equal to, or greater than any of the above lower limits.

[0131] For example, the lower limit of the density of high-density packing can be 3.00 g / cm³. 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 The approximate value, and its upper limit, can be 7 g / cm³. 36.5 g / cm 3 6 g / cm 3 5.5 g / cm 3 5 g / cm 3 4.5 g / cm 3 Or 4 g / cm 3 The density of high-density fillers can be greater than or equal to, or greater than any of the lower limits mentioned above; or it can be less than or equal to, or less than any of the upper limits mentioned above while being greater than or equal to, or greater than any of the lower limits mentioned above.

[0132] The density of the filler can be measured by known methods, and can be obtained, for example, based on the ASTM D792 standard.

[0133] For example, the lower limit of the weight ratio of low-density filler in the filler component can be approximately 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 can be approximately 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%, 52 wt%, 50 wt%, 48 wt%, 46 wt%, 44 wt%, 42 wt%, or 40 wt%. The weight ratio can be greater than or equal to, or greater than any of the lower limits mentioned above; less than or equal to, or less than any of the upper limits mentioned above; or less than or equal to, or less than any of the upper limits mentioned above while being greater than or equal to, or greater than any of the lower limits mentioned above.

[0134] In one instance, the low-density packing material can be a hydroxide packing material as described above.

[0135] Curable compositions can substantially comprise resin and filler components, and may include additional components if desired. In this case, there are no particular limitations on the types of components that can be included.

[0136] For example, one or two or more common components, 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.

[0137] Curable compositions can be prepared by mixing the components listed above. There are no particular limitations on the mixing method used, and any known mixing method for preparing compositions can be applied.

[0138] In one example, the curable composition may be the main component or the curing agent component of a two-component composition.

[0139] As a two-component composition comprising a main component and a curing agent, this specification discloses a two-component composition wherein either or both of the main component and the curing agent are curable compositions.

[0140] For example, the main component may contain at least a polyol and a filler component, wherein the polyol may be the aforementioned polyol, and the filler may be the aforementioned filler. Furthermore, the curing agent component may contain at least a polyisocyanate and a filler component, wherein the polyisocyanate may be the aforementioned polyisocyanate.

[0141] This specification also discloses the use of the curable composition or its cured product. For example, this application relates to products comprising a heating element and a material in contact with the heating element, wherein said material includes the above-described curable composition or its cured product.

[0142] There are no particular restrictions on the type of heating component here, and all components with heating characteristics that must be managed during use or storage can be applied. In such products, materials containing curable compositions or their cured products can be used as so-called TIM (thermal interface materials).

[0143] For example, various electrical and electronic products such as irons, washing machines, dryers, garment care equipment, electric shavers, microwave ovens, rice cookers, refrigerators, dishwashers, air conditioners, fans, humidifiers, air purifiers, mobile phones, walkie-talkies, televisions, radios, computers, or laptops, or battery products such as rechargeable batteries may include such heating components.

[0144] For example, in the product, a material comprising a curable composition or a cured product thereof can be used for transferring heat generated by a heating element to a cooling area. In this case, the material can dissipate the heat generated by the heating element. The heating element can be a battery cell or a battery module.

[0145] Beneficial effects

[0146] This specification discloses curable compositions. These curable compositions exhibit excellent storage stability even when containing fillers to achieve high thermal conductivity, without viscosity changes or inhomogeneities due to excess filler settling, etc. The curable compositions also exhibit both high thermal conductivity and storage stability even when using hydroxide fillers as fillers. This specification discloses the uses of these curable compositions. Detailed Implementation

[0147] In the following description, curable compositions and the like are specifically described by way of examples and comparative examples, but the scope of curable compositions and the like is not limited to the following examples.

[0148] 1. Assessment of thermal conductivity

[0149] The thermal conductivity of the curable composition was measured using the hot-disk method according to ISO 22007-2. Specifically, a mixture of the main component and the curing agent in a 1:1 volume ratio from the examples or comparative examples was placed into a mold with a thickness of approximately 7 mm, cured, and the thermal conductivity was measured in the through-plane direction using a hot-disk device. As specified in the standard (ISO 22007-2), the hot-disk device used was one that could check the thermal conductivity by measuring temperature changes (resistance changes) while a sensor with a nickel wire double helix structure was heated. Curing of the curable composition was carried out by holding the 1:1 volume ratio mixture of the main component and the curing agent at room temperature (approximately 25°C) for approximately 24 hours.

[0150] The main agent and curing agent components are mixed at a 1:1 volume ratio using a device 1, as shown in Figure 1, which connects two material cylinders 2a, 2b, and 2 and a static mixer 5. Each material cylinder 2, 2a, and 2b is a material cylinder (Sulzer, AB050-01-10-01) with a circular material injection section of 18 mm diameter, circular material discharge sections 4, 4a, and 4b of 3 mm diameter, a height of 100 mm, and an internal volume of 25 mL. The static mixer 5 is a stepped static mixer (Sulzer, MBH-06-16T) with material discharge sections 4, 4a, and 4b, circular receiving sections 6a and 6b of 3 mm diameter, a circular discharge section 7 of 2 mm diameter, and 16 other elements. The main agent and curing agent portions, respectively loaded into barrels 2a, 2b, and 2, are injected into the static mixer 5 at a constant speed of 1 mm / s by TA (Texture Analyzer) 3, 3a, and 3b, which act as pressure devices, and are mixed. The mixture is then discharged through the discharge section 7.

[0151] 2. Measurement of average particle size

[0152] The average particle size of the packing material mentioned in this specification is the D50 particle size, which is the particle size measured using a Malvern Mastersizer 3000 instrument according to ISO-13320 standard. Ethanol is used as the solvent during measurement. The incident laser is scattered by the packing material dispersed in the solvent. The intensity and directionality of the scattered laser vary depending on the size of the packing material, and this is analyzed using Mie theory to obtain the D50 particle size. Based on this analysis, a volume-based cumulative distribution can be obtained by converting it to the diameter of spheres with the same volume as each of the dispersed packing materials, and the average particle size (D50 particle size) can be obtained by setting the value at 50% of the cumulative volume in the distribution as the median.

[0153] 3. Evaluation of packing sphericity

[0154] Whether a packing material is spherical is assessed by measuring its sphericity. The sphericity of a packing material that is a three-dimensional particle is defined as the ratio (S' / S) of the surface area of ​​the particle (S) to the surface area (S') of a sphere with the same volume as the particle, and for actual particles, it is typically the average of the sphericity. Circularity is the ratio of the boundary (P) of a two-dimensional image of the particle to the boundary of a circle with the same area (A) as said image, which is theoretically obtained using the following formula. The value of sphericity ranges from 0 to 1, where, in the case of an ideal circle, sphericity is 1. In this specification, packing materials with a sphericity of 0.9 or greater are defined as spherical packing materials, and packing materials with a sphericity less than 0.9, such as amorphous packing materials, are defined as non-spherical packing materials. Such sphericity can also be measured using a Malvern particle shape analysis instrument (FPIA-3000).

[0155] <Circularity>

[0156] Circularity = 4πA / P 2

[0157] 4. Evaluation of packing density

[0158] The packing density is obtained by calculating the specific gravity of the packing according to ASTM D792 and multiplying the obtained specific gravity by 0.9976.

[0159] 5. Evaluation of the specific surface area of ​​the filler

[0160] The BET (Brunauer-Emett-Teller) specific surface area is calculated using the BET method by employing an adsorption curve obtained by adsorbing nitrogen onto the sample. The BET specific surface area is obtained using an ASAP 2020 (Accelerated Surface Area and Porosimetry System) instrument to adsorb nitrogen.

[0161] 6. Density assessment of curable compositions

[0162] The density of the curable composition was evaluated using the following method. A mixture of the main component and curing agent from the examples or comparative examples, in a 1:1 volume ratio, was injected into a mold and cured to form a cured product of a predetermined volume. The weight of the cured product was then measured. Subsequently, the density of the cured product was measured by both weight and volume. Here, the curing of the curable composition was performed in the same manner as in the thermal conductivity measurement.

[0163] 7. Assessment of weight-average molecular weight

[0164] Weight-average molecular weight (Mw) was measured using GPC (Gel permeation chromatography). In this specification, the unit of weight-average molecular weight is g / mol. The analytical sample was placed in a 20 mL vial and diluted with THF (tetrahydrofuran) to a concentration of approximately 20 mg / mL. After filtering the calibration standard and analytical sample through a syringe filter (pore size: 0.2 μm), the weight-average molecular weight was measured. Agilent Technologies' ChemStation was used as the analytical procedure, and the weight-average molecular weight (Mw) was obtained by comparing the elution time with a calibration curve. The measurement conditions for weight-average molecular weight are as follows:

[0165] <Measurement Conditions>

[0166] Instrument: Agilent Technologies 1200 Series

[0167] Column: Using Agilent Technologies' TL Mix. A & B

[0168] Solvent: THF

[0169] Column temperature: 40℃

[0170] Sample concentration: 20 mg / mL, injection 10 μL

[0171] MPs 364000, 91450, 17970, 4910, and 1300 were used as standard samples.

[0172] 8. Viscosity Measurement

[0173] The viscosity of the curable composition can be measured using a viscometer (Brookfield LV) and a 52Z rotor. The rotor is selected based on the viscosity measurement range. After zeroing the viscometer, install the rotor onto the rotor connector and the plate onto the plate connector. Adjust the rotor to create a constant gap between the rotor and the plate using the adjusting lever. Remove the plate and apply approximately 0.5 mL of the curable composition to the center of the removed plate. Reinstall the plate with the applied curable composition onto the plate connector and, after waiting until the torque value drops to zero, measure the viscosity for 3 minutes at approximately 25°C and 2.4 rpm. Take the final value after 3 minutes as the viscosity value of the curable composition.

[0174] 9. Storage stability assessment

[0175] The curable composition (either the main component or the curing agent component) was placed in a 30 mL dispenser syringe (Musach, PSY-30F) (diameter: approx. 26.2 mm, length: approx. 130 mm) and stored for 30 days while the dispenser syringe was kept vertical. This storage was conducted at room temperature (approx. 25°C) and atmospheric pressure (approx. 1 atm) without separate control of relative humidity. After storage, approximately 0.5 mL of the curable composition was collected from each of the upper and lower portions of the dispenser syringe. The viscosities of the upper and lower portions were determined as shown in “8. Viscosity Measurement” above, and the viscosity deviation was calculated by substituting the upper and lower viscosities into Equation 1 below. The storage stability and filler settling were thus determined from the results.

[0176] [Formula 1]

[0177] ΔV = 100 × (V L -V U ) / V U

[0178] In Equation 1, V U The measured viscosity of the upper curable composition, and V L The measured viscosity is for the lower curable composition.

[0179] Example 1

[0180] A two-component curable composition comprising a base agent and a curing agent is prepared as follows.

[0181] The main component is prepared by mixing resin component (a1), filler component (b1), dispersant (c), and catalyst (d) in a weight ratio of approximately 8.21:91.24:0.46:0.09 (a1:b1:c:d). These components are mixed in a planetary centrifugal mixer at 600 rpm and 500 rpm for approximately 3 minutes, and then defoamed again at 600 rpm and 200 rpm for approximately 3 minutes to prepare the main component.

[0182] As the resin component (a1), a polyester-based polyol (Capa) is used. TM 2043 (weight average molecular weight: approximately 400 g / mol). This polyol has an OH value of approximately 280 mg KOH / g and an acid value of less than approximately 0.25 mg KOH / g. The OH value is measured according to ASTM E 1899-08 standard. The filler component (b1) has an average particle size (D50 particle size) of approximately 80 μm and a BET specific surface area of ​​approximately 0.17 m². 2 The filler F1 is a non-spherical (amorphous) aluminum hydroxide (ATH) material with an average particle size (D50 particle size) of approximately 20 μm and a BET specific surface area of ​​approximately 0.14 m². 2 The filler F2 contains approximately spherical alumina particles per gram, with an average particle size (D50 particle size) of approximately 1.5 μm and a BET specific surface area of ​​approximately 2.0 m². 2 The filler F3, with a weight ratio of approximately 25:25:50, is prepared using non-spherical alumina filler F3 at a ratio of approximately 25:25:50 (F1:F2:F3).

[0183] DISPERBYK-111 (BYK) was used as a dispersant. Additionally, dibutyltin dilaurate was used as a catalyst.

[0184] The curing agent portion is prepared by mixing resin component (a2), filler component (b2), dispersant (c), and additive (e) in a weight ratio of approximately 8.96:89.55:0.5:1 (a2:b2:c:e). These components are mixed in a planetary centrifugal mixing vessel at 600 rpm and 500 rpm for approximately 3 minutes, and then defoamed again at 600 rpm and 200 rpm for approximately 3 minutes to prepare the curing agent portion.

[0185] Hexamethylene diisocyanate (HDI) was used as resin component (a2). Filler component (b2) consisted of filler F1 used in the main component, filler F2 used in the main component, and filler with an average particle size (D50 particle size) of approximately 1.5 μm and a BET specific surface area of ​​approximately 3.5 m². 2 The filler F4, approximately 1 g / g of non-spherical (amorphous) aluminum hydroxide (ATH), was prepared by mixing in a weight ratio of 40:40:20 (F1:F2:F4).

[0186] The weighted average particle size of all packing components (b2) is approximately 40.3 μm, the weighted average particle size of hydroxide packing (ATH) is approximately 53.8 μm, the weighted average particle size of oxide packing (alumina) is approximately 20 μm, the weighted average particle size of spherical packing is approximately 20 μm, and the weighted average particle size of non-spherical packing is approximately 53.8 μm.

[0187] The weighted average BET specific surface area of ​​all filler components (b2) is approximately 0.82 m². 2 The weighted average BET specific surface area of ​​the hydroxide filler is approximately 1.28 m² / g. 2 The weighted average BET specific surface area of ​​the oxide filler (alumina) is approximately 0.14 m² / g. 2 The weighted average BET specific surface area of ​​the spherical packing is approximately 0.14 m² / g. 2 The weighted average BET specific surface area of ​​the non-spherical packing is approximately 1.28 m² / g. 2 Approximately / g.

[0188] Disperbyk-111 (byk) was used as a dispersant. Additionally, VTMO (vinyl trimethoxysilane) was used as an additive.

[0189] Example 2

[0190] The main agent component was prepared in the same manner as in Example 1, except that the filler component (b1) used in the preparation of the main agent component was obtained by mixing fillers F1 to F3 from Example 1 in a weight ratio of 30:30:40 (F1:F2:F3). The curing agent component was the same as that used in Example 1.

[0191] Example 3

[0192] The main agent component was prepared in the same manner as in Example 1, except that the filler component (b1) used in the preparation of the main agent component was obtained by mixing fillers F1 to F3 from Example 1 in a weight ratio of 32.5:32.5:35 (F1:F2:F3). The curing agent component was the same as that used in Example 1.

[0193] Comparative Example 1

[0194] The main agent component was prepared in the same manner as in Example 1, except that the filler component (b1) of the main agent component was a filler component obtained by mixing fillers F1 to F3 in a weight ratio of 20:20:60 (F1:F2:F3). The curing agent component was the same as in Example 1.

[0195] Comparative Example 2

[0196] The main agent component was prepared in the same manner as in Example 1, except that the filler component (b1) used in the preparation of the main agent component was obtained by mixing fillers F1 to F3 from Example 1 in a weight ratio of 35:35:30 (F1:F2:F3). The curing agent component was the same as that used in Example 1.

[0197] Comparative Example 3

[0198] The main agent component was prepared in the same manner as in Example 1, except that the filler component (b1) used in the preparation of the main agent component was obtained by mixing fillers F1 to F3 from Example 1 in a weight ratio of 40:40:20 (F1:F2:F3). The curing agent component was the same as that used in Example 1.

[0199] Comparative Example 4

[0200] The main agent component was prepared in the same manner as in Example 1, except that the filler component (b1) used in the preparation of the main agent component was obtained by mixing fillers F1 to F3 from Example 1 in a weight ratio of 40:20:40 (F1:F2:F3). The curing agent component was the same as that used in Example 1.

[0201] Comparative Example 5

[0202] The difference lies in the filler component (b1) used in the preparation of the main agent, which uses a filler with an average particle size (D50 particle size) of approximately 80 μm and a BET specific surface area of ​​approximately 0.05 m². 2The filler composition was obtained by mixing filler F5 of approximately / g of spherical alumina with fillers F2 and F3 of Example 1 in a weight ratio of 25:25:50 (F5:F2:F3).

[0203] The weighted average particle size and weighted average BET specific surface area of ​​the filler components used in the main component portion of the curable compositions of the Examples and Comparative Examples are summarized and described in Table 1 below. In Table 1, the average particle size is the weighted average particle size, and the specific surface area is the weighted average BET specific surface area.

[0204] In Table 1, particle size is measured in μm, and BET specific surface area is measured in m². 2 / g.

[0205] In Table 1, ΔW1 is the ratio (F / F3) of the weight of the filler with the smallest average particle size in the mixed filler component used to prepare the main agent to the weight (F) of the remaining filler, and ΔW2 is the ratio ((F1 or F5) / F2) of the weight of the filler with the largest average particle size in the mixed filler component used to prepare the filler component to the weight (F2) of the filler with the second largest average particle size.

[0206] [Table 1]

[0207]

[0208] For the main component of the curable compositions of the examples and comparative examples, ΔV and V are determined according to Formula 1 as described in "9. Storage Stability Assessment" above. U and V L The thermal conductivity of the cured product, determined for the mixture of the main component and the curing agent, is described in Table 2 below. In Table 2, ΔV is the absolute value of the above ΔV. In Table 2, viscosity V... U and V L The unit for is Pa·second, the unit for ΔV is %, and the unit for thermal conductivity is W / m·K.

[0209] [Table 2]

[0210]

[0211] According to Table 2, it can be determined that the main component of the embodiment prevents the sedimentation of the filler component even when it contains an excess of filler component, thereby ensuring storage stability, and it can be determined that its cured product exhibits high thermal conductivity.

[0212] In Comparative Examples 1 and 4, sedimentation of the filler components was prevented to some extent, but high thermal conductivity could not be ensured. In Comparative Examples 2, 3 and 5, due to severe sedimentation of the filler components, large deviations occurred between the upper and lower viscosity.

Claims

1. A curable composition comprising a resin component and packing components, in which The filler component has a weight ratio of 70% or more, and The filler component comprises hydroxide filler, and The curable composition forms a cured product with a thermal conductivity of 3.0 W / m·K or greater, wherein In Equation 1 below, the absolute value of ΔV is 10% or less: [Formula 1] ΔV=100×(V L -V U ) / V U in, V L and V U The lower and upper viscosities are respectively the lower and upper viscosities of the curable composition after it has been held at 25°C for 30 days in a 30 mL dispenser syringe with a diameter of 26.2 mm and a length of 130 mm in a vertical position.

2. A curable composition comprising a resin component and packing components, in which The filler component has a weight percentage of 70% or more. The filler component comprises hydroxide filler, and The weighted average BET specific surface area of ​​the filler component is 0.75 m². 2 / g or larger, and The curable composition forms a cured product with a thermal conductivity of 3.0 W / m·K or greater.

3. The curable composition according to claim 1, wherein the weighted average BET specific surface area of ​​the filler component is 0.75 m². 2 / g or larger.

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

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

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

7. The curable composition according to claim 6, wherein the weighted average particle size of the non-hydroxide filler is 50 μm or less.

8. The curable composition according to claim 6, wherein the non-hydroxide filler is an oxide filler or a nitride filler.

9. The curable composition according to claim 1 or 2, wherein the weighted average BET specific surface area of ​​the hydroxide filler is 0.01 m². 2 / g to 1 m 2 Within the range of / g.

10. The curable composition of claim 6, wherein the weighted average BET specific surface area of ​​the non-hydroxide filler in the filler component is 0.4 m². 2 / g or larger.

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

12. The curable composition according to claim 11, wherein ΔW1 in formula 2 is in the range of 0.5 to 3: [Equation 2] ΔW1=W 其他 / IN T in, W T The weight of the packing material with the smallest average particle size in the mixed packing, and W 其他 To subtract W from the total weight of the filler components T The value obtained.

13. The curable composition according to claim 11, wherein ΔW2 in formula 3 is in the range of 0.5 to 2: [Formula 3] ΔW2=W F / IN S in, W F The weight of the packing material with the largest average particle size in the mixed packing, and W S The weight of the packing material with the second largest average particle size in the mixed packing.

14. The curable composition of claim 12, wherein the filler with the smallest average particle size in the mixed filler has an average particle size in the range of 0.1 μm to 10 μm and a particle size in the range of 1 μm. 2 / g to 10 m 2 BET specific surface area in the range of / g.

15. The curable composition of claim 12, wherein the filler with the largest average particle size in the mixed filler has an average particle size of 60 μm or greater and is within 0.1 μm. 2 / g to 1 m 2 BET specific surface area in the range of / g.

16. The curable composition of claim 12, wherein the filler with the largest average particle size in the mixed filler is a hydroxide filler.

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

18. A two-component composition comprising: a main component containing a main resin; and The curing agent portion containing the curing agent, wherein The main component or the curing agent component is a curable composition according to claim 1 or 2.

19. A product comprising a heating element and a material in contact with said heating element. in The material includes the curable composition according to claim 1 or 2, or its cured product.

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

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