Curable Composition And Two-Component Curable Composition

Abstract

The present application may provide a curable composition having excellent storage stability with no change in physical properties such as viscosity or hardness during storage, and a two-component curable composition comprising such a curable composition. Additionally, the present application may provide a curable composition having excellent storage stability without using separate additives or without a surface treatment process of a thermally conductive filler, and a two-component curable composition comprising such a curable composition.

Description

Technology Field

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0127591 filed September 29, 2020, and all contents disclosed in the document of said Korean patent application are incorporated herein as part of this specification.

[0003] Technology field

[0004] The present application is an invention relating to a curable composition and a two-component curable composition. Background Technology

[0005] Thermal dissipation materials are used in various fields. Taking vehicles as an example, thermal dissipation materials can be used to manage heat generated from battery modules and on-board chargers (OBCs) embedded in rechargeable electric vehicles. Additionally, thermal dissipation materials are applied to components that consume high power and generate significant heat, such as LED modules, to extend their lifespan.

[0006] Silicone-based resin compositions have excellent heat resistance and can be used as heat dissipation materials. In order to achieve excellent thermal conductivity performance in such silicone-based resin compositions, inorganic hydroxide fillers may be added.

[0007] However, if inorganic hydroxide fillers are used without surface treatment, highly reactive inorganic hydroxide fillers react with curing agents, etc., within the resin composition. Consequently, as time passes, the viscosity and hardness of the resin composition or the cured product may deviate from the designed range, which may lead to a problem of reduced long-term storage stability.

[0008] To address these issues, there is a method of surface-treating inorganic hydroxide fillers and mixing them with a silicone-based resin composition; however, since this method requires a significant amount of time and cost, a method is required to ensure the long-term storage stability of the resin composition without surface treatment of the fillers. The problem to be solved

[0009] The present application aims to provide a curable composition having excellent storage stability with no change in physical properties such as viscosity or hardness during storage, and a two-component curable composition comprising such a curable composition.

[0010] In addition, the present application aims to provide a curable composition having excellent storage stability without using separate additives or a surface treatment process of a thermally conductive filler, and a two-component curable composition comprising such a curable composition. means of solving the problem

[0011] Among the physical properties mentioned in this specification, those properties whose measurement temperature affects the property are properties measured at room temperature, unless otherwise specifically defined.

[0012] In this specification, the term "room temperature" refers to a 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, about 15°C, about 18°C, about 20°C, about 23°C, or about 25°C. Additionally, unless otherwise specifically defined in this specification, the unit of temperature is °C.

[0013] In this specification, the term alkenyl group may mean a straight-chain, branched-chain, or cyclic alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless specifically otherwise defined.

[0014] In this specification, the term alkyl group or alkoxy group may mean a straight-chain, branched-chain, or cyclic alkyl group or alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless specifically otherwise defined.

[0015] In this specification, the term "aryl group" may refer to a compound comprising a benzene structure, a compound comprising a structure in which two or more benzenes are connected by a linker, a compound comprising a structure in which two benzenes each share one or two carbon atoms and are condensed or bonded, or a monovalent residue derived from a derivative of any of the aforementioned compounds, unless specifically defined otherwise. The scope of "aryl group" as used in this specification may include not only functional groups commonly referred to as aryl groups, but also so-called aralkyl groups or arylalkyl groups. An aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. Examples of aryl groups may include a phenyl group, dichlorophenyl, chlorophenyl, phenylethyl group, phenylpropyl group, benzyl group, tolyl group, xylyl group, or naphthyl group.

[0016] The above alkenyl group, alkoxy group, alkyl group, or aryl group, etc., may optionally be substituted by one or more substituents. Examples of such substituents include halogens such as chlorine or fluorine, epoxy groups such as glycidyl groups, epoxyalkyl groups, glycidoxyalkyl groups or alicyclic epoxy groups, acryloyl groups, methacryloyl groups, isocyanate groups, thiol groups, or monovalent hydrocarbon groups, but are not limited thereto.

[0017] In this specification, the term M unit is typically (R3SiO 1 / 2 It refers to the so-called monofunctional siloxane unit, which is sometimes denoted as ), and the term D unit is typically (R2SiO2 / 2 It refers to the so-called difunctional siloxane unit, which is sometimes denoted as ), and the term T unit is usually (RSiO 3 / 2 It refers to the so-called trifunctional siloxane unit, which is sometimes denoted as ), and the term Q unit is typically (SiO 4 / 2 It may refer to so-called tetrafunctional siloxane units that are sometimes represented as ). In the formula of each of the above siloxane units, R is a functional group bonded to silicon (Si), and may be, for example, hydrogen, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an epoxy group.

[0018] The curable composition of the present application may comprise an alkenyl group-containing polyorganosiloxane component, a silicon-bonded hydrogen-containing polyorganosiloxane component, and a filler component having a filler having a hydroxyl group on its surface. The curable composition of the present application is cured by a reaction (a hydrosilylation reaction product) between the alkenyl group of the alkenyl group-containing polyorganosiloxane component and the hydrogen of the silicon-bonded hydrogen-containing polyorganosiloxane component.

[0019] In one example, the above curable composition may be a one-component resin composition, a main component of a two-component resin composition, a curing agent composition of a two-component resin composition, or a mixture of the main component and the curing agent composition of a two-component resin composition. A one-component resin composition is a resin composition in which the curable components are stored in a mixed state, and a two-component resin composition is a resin composition in which the curable components are stored separately as a main component composition and a curing agent composition in which they are physically separated. In the case of a two-component resin composition, the main component and the curing agent composition are mixed under conditions where curing can occur at the time of use.

[0020] In this specification, the term polyorganosiloxane component may be a mixture of polyorganosiloxanes and / or a mixture of polyorganosiloxanes and siloxane monomers. In a more specific example, the polyorganosiloxane component may be the product of a polymerization reaction performed to obtain a specific desired polyorganosiloxane or a mixture of two or more products of said polymerization reaction.

[0021] As the alkenyl group-containing polyorganosiloxane component in the curable composition, known polyorganosiloxane components may be used without special limitations. In one example, the polyorganosiloxane component may be a polyorganosiloxane component including a linear polyorganosiloxane.

[0022] As is known, linear polyorganosiloxane is a polyorganosiloxane with a structure in which both ends of a chain structure composed of D units are blocked by M units.

[0023] Linear polyorganosiloxane is a polyorganosiloxane with a structure in which both ends of a chain structure composed of D units are blocked by M units.

[0024] In the above structure, various types of units can be used as the D unit. For example, as the D unit, the so-called dialkylsiloxane unit (R2SiO2) 2 / 2 Difunctional siloxane units in which R are all alkyl groups in the structure), diarylsiloxane units (R2SiO2) 2 / 2 Difunctional siloxane unit in which R is entirely an aryl group in the structure), dialkenylsiloxane unit (R2SiO2) 2 / 2 Difunctional siloxane units in which all R groups in the structure are alkenyl groups), alkylarylsiloxane units (R2SiO2) 2 / 2 A difunctional siloxane unit in which one R is an alkyl group and the other R is an aryl group in the structure), an alkylalkenylsiloxane unit (R2SiO2) 2 / 2 A difunctional siloxane unit in which one R is an alkyl group and the other R is an alkenyl group in the structure) and an aryl alkenyl siloxane unit (R2SiO 2 / 2At least one unit selected from the group consisting of difunctional siloxane units in which one R is an alkenyl group and the other R is an aryl group in the structure may be applied.

[0025] Suitable D units include the dialkylsiloxane unit (R2SiO2) among the above. 2 / 2 Difunctional siloxane units in which R are all alkyl groups in the structure) and / or alkylalkenylsiloxane units (R2SiO2) 2 / 2 A difunctional siloxane unit in which one R is an alkyl group and the other R is an alkenyl group in the structure can be exemplified.

[0026] In the structure of linear polyorganosiloxanes, the M units at both ends of the chain structure composed of D units are, for example, alkenyldialkylsiloxane units (R3SiO2). 1 / 2 A monofunctional siloxane unit in which one of the R groups in the structure is an alkenyl group and the other two are alkyl groups) and / or a trialkylsiloxane unit (R3SiO2) 1 / 2 Examples may include monofunctional siloxane units in which R is an alkyl group in the structure. For example, in the case of a structure in which both ends are terminated by alkenyl groups, an alkenyldialkyl siloxane unit may be used as the M unit.

[0027] In one example, as a polyorganosiloxane having an alkenyl group, the D unit of the main chain structure of the linear polyorganosiloxane is a dialkylsiloxane unit (R2SiO 2 / 2 Difunctional siloxane units in which R are all alkyl groups in the structure) and / or alkylalkenylsiloxane units (R2SiO2) 2 / 2 It is a difunctional siloxane unit in which one R is an alkyl group and the other R is an alkenyl group in the structure), and the M units at both ends are alkenyldialkylsiloxane units (R3SiO2). 1 / 2 Polyorganosiloxanes that are monofunctional siloxane units in which one of the R groups in the structure is an alkenyl group and the other two are alkyl groups can be used.

[0028] When two or more types of D units are used as D units of the above main chain, the form of the main chain may be a random copolymer, a block copolymer, or a gradient copolymer main chain form.

[0029] In one example, as the polyorganosiloxane component, a component represented by the following average unit formula A may be used.

[0030] The term average unit formula is a unit formula that indicates the ratio of the moles of each siloxane unit present when the total number of moles of all siloxane units (M, D, T, and Q units) present in the polyorganosiloxane component is converted to 1.

[0031] [Average Unit Formula A]

[0032] (R 1 R 2 2SiO 1 / 2 ) a (R 2 3SiO 1 / 2 ) b (R 1 R 2 SiO 2 / 2 ) c (R 2 2SiO 2 / 2 ) d

[0033] R in average unit formula A 1 is an alkenyl group, and R 2 is an alkyl group or an aryl group, a+b+c+d is 1, (a+b) is a number in the range of 0.001 to 0.05, (c+d) is a number in the range of 0.7 to 0.999, and b / a and c / d are each independently numbers in the range of 0 to 10.

[0034] In the average unit formula A, (a+b) may be 0.007 or greater or 0.009 or greater, or 0.045 or less, 0.04 or less, 0.035 or less, 0.03 or less, 0.025 or less, 0.02 or less, or 0.015 or less.

[0035] In the average unit formula A, (c+d) may be 0.75 or more, 0.8 or more, 0.85 or more, 0.9 or more, or 0.95 or more, or 0.997 or less, 0.995 or less, 0.993 or less, or 0.991 or less.

[0036] In the average unit formula A, b / a may be approximately 0 to 9, 0 to 8, 0 to 7, 0 to 6, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 0 to 1, or 0 to 0.5 in other examples, or it may be 0.

[0037] In the average unit formula A, c / d may be approximately 0 to 9, 0 to 8, 0 to 7, 0 to 6, 0 to 5, 0 to 4, 0 to 3, 0 to 2, 0 to 1, or 0 to 0.5 in other examples, or it may be 0.

[0038] In one example, the alkenyl group-containing polyorganosiloxane component may include a polyorganosiloxane represented by the following chemical formula 1.

[0039] [Chemical Formula 1]

[0040]

[0041] In Chemical Formula 1, R5 is an alkenyl group, R6 is an alkyl or aryl group, and n is a number in the range of 30 to 300. In Chemical Formula 1, n is 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, 110 or more, 120 or more, 130 or more, 140 or more, 150 or more, 160 or more, 170 or more, 180 or more, 190 or more, 200 or more, 210 or more, 220 or more, 230 or more, 240 or more, or 250 or more, or 290 or less, 280 or less, 270 or less, 260 or less, 250 or less, 240 or less, 230 or less, 220 or less, 210 or less, 200 or less, 190 or less, 180 or less, 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 120 or less, It may be 110 or less, or about 100 or less.

[0042] In the definition of Chemical Formula 1 above, the specific types of alkenyl groups, alkyl groups, aryl groups, etc. are as described in the introduction of the means for solving the problem of this specification.

[0043] The above alkenyl group-containing polyorganosiloxane component may contain alkenyl groups in an amount of about 0.05 to 5 mmol / g. In other examples, the ratio of the alkenyl groups may be about 0.1 mmol / g or more, 0.15 mmol / g or more, 0.2 mmol / g or more, 0.25 mmol / g or more, or 4 mmol / g or less, 3 mmol / g or less, 2 mmol / g or less, 1 mmol / g or less, 0.5 mmol / g or less, or 0.3 mmol / g or less. The above ratio is a value calculated by determining the ratio of alkenyl groups of the alkenyl group-containing polyorganosiloxane component within the liquid curing agent composition excluding the filler component.

[0044] The ratio of the alkenyl groups above may be changed according to the specific use of the curable composition, and if it satisfies the prescribed range, it can be mixed with a filler component to secure the desired viscosity.

[0045] For example, when the curable composition is a curing agent composition of a two-component curable composition, the ratio of the alkenyl groups may be, within the above range, additionally about 0.1 mmol / g or more, 0.15 mmol / g or more, 0.2 mmol / g or more, 0.25 mmol / g or more, or 4 mmol / g or less, 3 mmol / g or less, 2 mmol / g or less, 1 mmol / g or less, 0.5 mmol / g or less, or 0.3 mmol / g or less.

[0046] In other examples, when the curable composition is a mixture of a main component and a curing agent composition of a two-component curable composition or a one-component curable composition, the ratio of the alkenyl groups may be further adjusted within the above range to 0.1 mmol / g or more, 0.15 mmol / g or more, 0.2 mmol / g or more, 0.25 mmol / g or more, 0.3 mmol / g or more, or 0.35 mmol / g or more, and / or within the range of 4.5 mmol / g or less or 4 mmol / g or less.

[0047] The content of alkenyl groups and silicon-bonded hydrogens of the polyorganosiloxane component mentioned in this specification are as described in the examples below with respect to the polyorganosiloxane component. 1 H NMR and / or 29 This is a value obtained through Si NMR analysis. This method differs from the value theoretically obtained through the chemical formula of the polyorganosiloxane included in the polyorganosiloxane component. That is, because there may be various types of polyorganosiloxane within the polyorganosiloxane component that belong to the same category of chemical formulas but have different detailed structures (for example, multiple polyorganosiloxanes with different n values ​​may exist within the structure of Chemical Formula 1), it is not possible to determine the exact ratio between curable functional groups (ratio of alkenyl groups and silicon-bonded hydrogens) using this method.

[0048] The above ratio plays an important role in securing the desired storage stability (suppression of changes in viscosity and hardness over time) and thixotropy, etc., and this is the above 1 H NMR and / or 29 It must be determined based on the results of Si NMR analysis.

[0049] In one example, the polyorganosiloxane having the alkenyl group may have a number average molecular weight (Mn) in the range of 2500 g / mol to 20000 g / mol. In another example, the number average molecular weight (Mn) of the polyorganosiloxane having the alkenyl group may be 3000 g / mol or more, 3500 g / mol or more, 4000 g / mol or more, 4500 g / mol or more, 5000 g / mol or more, or 5500 g / mol or more, or 19000 g / mol or less, 18000 g / mol or less, 17000 g / mol or less, 16000 g / mol or less, 15000 g / mol or less, or 14000 g / mol or less.

[0050] The polyorganosiloxane component containing silicon-bonded hydrogen in the curable composition may also be a known material without special limitations. For example, as the polyorganosiloxane component, a linear polyorganosiloxane, that is, a polyorganosiloxane with a structure in which both ends of a chain structure consisting of D units are blocked by M units, may be used.

[0051] In the above structure, various types of units can be used as the D unit. For example, as the D unit, the so-called dialkylsiloxane unit (R2SiO2) 2 / 2 Difunctional siloxane units in which R are all alkyl groups in the structure), diarylsiloxane units (R2SiO2) 2 / 2 Difunctional siloxane unit in which R is an all-aryl group in the structure), dihydrogensiloxane unit (R2SiO2) 2 / 2 Difunctional siloxane unit in which R is all hydrogen in the structure), alkylarylsiloxane unit (R2SiO 2 / 2A difunctional siloxane unit in which one R is an alkyl group and the other R is an aryl group in the structure), an alkylhydrogensiloxane unit (R2SiO2) 2 / 2 A difunctional siloxane unit in which one R is an alkyl group and the other R is hydrogen in the structure) and an arylhydrogensiloxane unit (R2SiO2) 2 / 2 At least one unit selected from the group consisting of difunctional siloxane units in which one R is hydrogen and the other R is an aryl group in the structure may be applied.

[0052] Suitable D units include the dialkylsiloxane unit (R2SiO2) among the above. 2 / 2 Difunctional siloxane units in which R are all alkyl groups in the structure) and / or alkylhydrosiloxane units (R2SiO2) 2 / 2 A difunctional siloxane unit in which one R is an alkyl group and the other R is hydrogen in the structure can be exemplified.

[0053] In the structure of linear polyorganosiloxanes, the M units at both ends of the chain structure composed of D units are, for example, hydrogendialkylsiloxane units (R3SiO 1 / 2 A monofunctional siloxane unit in which one of the R groups in the structure is hydrogen and the other two are alkyl groups) and / or a trialkylsiloxane unit (R3SiO2) 1 / 2 Examples may include monofunctional siloxane units in which R in the structure is entirely an alkyl group. For instance, in the case of a structure in which both ends are terminated by silicon-bonded hydrogen, a hydrogendialkyl siloxane unit may be used as the M unit.

[0054] In one example, as the silicon-bonded hydrogen-containing polyorganosiloxane component, a component represented by the following average unit formula B may be used.

[0055] [Average Unit Formula B]

[0056] (HR 3 2SiO 1 / 2 ) a (R 3 3SiO 1 / 2 ) b (R 3 2SiO2 / 2 ) c (HR 3 SiO 2 / 2 ) d

[0057] R in the average unit formula B 3 is an alkyl group or an aryl group, and a+b+c+d is 1, a is a number within the range of 0.001 to 0.2, b is a number within the range of 0.01 to 0.8, c is a number within the range of 0.01 to 0.7, and d may be a number within the range of 0.001 to 0.4.

[0058] In other examples, the above a may be a number within the range of 0.003 or more, 0.005 or more, 0.007 or more, 0.009 or more, 0.01 or more, 0.03 or more, 0.05 or more, 0.07 or more, or 0.085 or more, or within the range of 0.15 or less or 0.1 or less.

[0059] In other examples, the above b may be a number within the range of 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.3 or more, 0.35 or more, or 0.4 or more, or 0.7 or less, 0.6 or less, 0.5 or less, or 0.45 or less.

[0060] In other examples, the above c may be a number within the range of 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, or 0.3 or more, or may be a number within the range of 0.65 or less, 0.6 or less, 0.55 or less, 0.5 or less, 0.45 or less, 0.4 or less, or 0.35 or less.

[0061] In other examples, the above d may be within the range of 0.003 or more, 0.005 or more, 0.007 or more, 0.009 or more, 0.01 or more, 0.03 or more, 0.05 or more, 0.07 or more, 0.09 or more, 0.11 or more, or 0.13 or more, or may be a number within the range of 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less. In one example, the silicon-bonded hydrogen-containing polyorganosiloxane component may include a first polyorganosiloxane component comprising a polyorganosiloxane of Formula 2 below and a second polyorganosiloxane component comprising a polyorganosiloxane of Formula 3.

[0062] [Chemical Formula 2]

[0063]

[0064] In Formula 2, R3 is an alkyl group or an aryl group, and m is a number within the range of 4 to 25. In Formula 2, m may be 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 11 or more, 12 or more, 13 or more, or 14 or more, or 23 or less, 21 or less, 19 or less, 17 or less, 15 or less, 13 or less, 11 or less, or 9 or less.

[0065] [Chemical Formula 3]

[0066]

[0067] In Chemical Formula 3, R4 is an alkyl group or an aryl group, p is a number within the range of 20 to 60, and q is a number within the range of 3 to 20. In Chemical Formula 3, p may be 21 or more, 22 or more, 23 or more, 24 or more, 25 or more, 26 or more, 27 or more, 28 or more, 29 or more, or 30 or more, or 55 or less, 50 or less, 45 or less, or 40 or less in other examples. Additionally, in Chemical Formula 3, q ​​may be 4 or more, 6 or more, 7.5 or more, 9 or more, or 11 or more, or 18 or less, 17 or less, 16 or less, 15 or less, or 14 or less in other examples.

[0068] The specific types of alkyl and aryl groups in the above Chemical Formula 2 or Chemical Formula 3 are as described in the introduction of the means for solving the problem of this specification.

[0069] The molar content of silicon-bonded hydrogen in the first polyorganosiloxane component may be 0.5 to 10 mmol / g. In another example, the first polyorganosiloxane component may contain silicon-bonded hydrogen in an amount of 1.2 mmol / g or more, 1.4 mmol / g or more, 1.6 mmol / g or more, 1.8 mmol / g or more, 2 mmol / g or more, 2.2 mmol / g or more, 2.4 mmol / g or more, or 2.6 mmol / g or more, or 9 mmol / g or less, 8 mmol / g or less, 7 mmol / g or less, 6 mmol / g or less, 5 mmol / g or less, or 4 mmol / g or less.

[0070] The molar content of silicon-bonded hydrogen in the second polyorganosiloxane component may be 0.5 to 6 mmol / g. In another example, the second polyorganosiloxane component may contain silicon-bonded hydrogen in an amount of 1 mmol / g or more, 2 mmol / g or more, 3 mmol / g or more, or 4 mmol / g or more, or 5.5 mmol / g or less, 5 mmol / g or less, or 4.5 mmol / g or less.

[0071] In one example, when the silicon-bonded hydrogen-containing polyorganosiloxane component comprises both the first polyorganosiloxane component and the second polyorganosiloxane component, the ratio (H1 / H2) of the moles of silicon-bonded hydrogen (H2) of the second polyorganosiloxane component to the moles of silicon-bonded hydrogen (H1) of the first polyorganosiloxane component may be within the range of 0.5 to 10.

[0072] The above ratio (H1 / H2) may be 1 or more, 1.5 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, or 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4.5 or less in other examples.

[0073] In the curable composition, the ratio (H / Ak) of the molar number of silicon-bonded hydrogens (H) of the silicon-bonded hydrogen-containing polyorganosiloxane component to the molar number of alkenyl groups (Ak) of the alkenyl group-containing polyorganosiloxane component can be controlled within a range of 2 to 10. In other examples, the range can be controlled to be 2.1 or more, 2.2 or more, 2.3 or more, 2.4 or more, 2.5 or more, 2.6 or more, 2.7 or more, or 2.8 or more, or 9 or less, 8 or less, or 7 or less.

[0074] The above ratio may be changed depending on the specific use of the above-mentioned curable composition.

[0075] For example, when the above ratio is a curing agent composition of a two-component curable composition, the above ratio may be further adjusted within the above range to a range of 3 or more, 3.5 or more, 4 or more, 4.5 or more, 5 or more, 5.5 or more, or 6 or more, and / or within a range of 9 or less, 8.5 or less, 8 or less, 7.5 or less, or 7 or less.

[0076] In other examples, if the curable composition is a mixed composition of a main component and a curing agent composition of a two-component curable composition or a one-component composition, the ratio may be further adjusted within the above range to a range of 2.2 or more, 2.4 or more, 2.6 or more, or 2.8 or more, and / or a range of 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0077] When a thermally conductive filler is applied as a filler in the above-mentioned curable composition, heat dissipation or thermal conductivity can be secured for the curable composition or the cured product.

[0078] The above thermally conductive filler is a filler that enables the curable composition to which the above filler is applied to form a cured product having a thermal conductivity of about 1 W / mK or more. The thermal conductivity of the above cured product may be about 1.2 W / mK or more, 1.4 W / mK or more, 1.6 W / mK or more, or 1.8 W / mK or more, or about 400 W / mK or less, about 350 W / mK or less, about 300 W / mK or less, 200 W / mK or less, 100 W / mK or less, 50 W / mK or less, 10 W / mK or less, 8 W / mK or less, 6 W / mK or less, 4 W / mK or less, or about 2 W / mK or less.

[0079] The filler component of the present application may have a filler having hydroxyl groups on its surface. In one example, the filler is aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), calcium hydroxide (Ca(OH)2) and hydromagnesite (Mg5(CO3)4(OH) 2· It may be one or more selected from the group consisting of 4H2O). These fillers have excellent thermal conductivity and low specific gravity, which is advantageous for lightweighting. There are no special restrictions on the shape of the filler that can be applied, and for example, spherical fillers, fillers in the shape of needles or plates, or other amorphous fillers may be used.

[0080] In one example, a filler having hydroxyl groups on its surface may have an average particle size in the range of 0.001 μm to 100 μm. The average particle size is a D50 particle size measured in the manner described in the examples below. The average particle size of the above filler is, in other examples, 0.005 μm or more, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.5 μm or more, 0.8 μm or more, 1 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, 35 μm or more, 40 μm or more, or 45 μm or more, or 95 μm or less, 90 μm or less, 85 μm or less, 80 μm or less, 75 μm or less, 70 μm or less, 65 μm or less, 60 μm or less, 55 μm or less, 50 μm or less, 45 μm or less, 40 μm or less, 35 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, It may be 15 μm or less, 10 μm or less, or about 5 μm or less.

[0081] In order to secure appropriate filling properties and the desired physical properties, a mixture of at least two types of fillers with different average particle sizes may be used as the filler. For example, as the filler, a first filler with an average particle size of 20 μm or more and a second filler with an average particle size of 10 μm or less may be used within the aforementioned range.

[0082] In other examples, the average particle size of the first filler may be 25 μm or more, 30 μm or more, 35 μm or more, 40 μm or more, or 45 μm or more, or 100 μm or less, 95 μm or less, 90 μm or less, 85 μm or less, 80 μm or less, 75 μm or less, 70 μm or less, 65 μm or less, 60 μm or less, or 55 μm or less.

[0083] In addition, the average particle size of the second filler may be 0.001 μm or more, 0.005 μm or more, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.5 μm or more, or 0.8 μm or more, or 10 μm or less, 8 μm or less, 6 μm or less, 4 μm or less, or 3 μm or less.

[0084] When the first and second fillers are applied simultaneously, the ratio (D1 / D2) based on the average particle size (D1) of the first filler and the average particle size (D2) of the second filler may be in the range of 2 to 200. In other examples, the ratio (D1 / D2) may be 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 35 or more, 40 or more, or 45 or more, or 170 or less, 150 or less, 130 or less, 110 or less, 95 or less, 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, or 55 or less.

[0085] When the first and second fillers are applied simultaneously, the ratio (W1 / W2) based on the weight (W1) of the first filler used and the weight (W2) of the second filler used may be in the range of 0.5 to 10. In other examples, the ratio (W1 / W2) may be 1 or more, 1.5 or more, or 2 or more, or 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0086] The above filler component may be included in a range of 200 to 900 parts by weight per 100 parts by weight of the alkenyl group-containing polyorganosiloxane component of the curable composition. Additionally, the above filler component may be included in a range of 1,000 to 30,000 parts by weight per 100 parts by weight of the silicon-bonded hydrogen-containing polyorganosiloxane component of the curable composition.

[0087] If the above range is satisfied, excellent heat dissipation characteristics can be secured, while simultaneously improving the adhesion between the metal and the curable composition and ensuring the long-term storage stability of the curable composition.

[0088] In one example, the filler component may be included in an amount of 50 to 75 volume% based on the total volume of the curable composition. The volume ratio can be calculated by taking into account the mass ratio of each component included in the curing agent composition and their densities, and components that are not included in the cured product of the final curing agent composition (e.g., volatile components or solvents, etc.) are not taken into account in the calculation.

[0089] The curable composition may include other components additionally required to the above components.

[0090] For example, the above-mentioned curable composition may further include a catalyst, for example, an addition reaction catalyst. The type of catalyst is not particularly limited, but, for example, a platinum-based catalyst may be used, and known or commercially available platinum-based catalysts may be used. There is no particular limitation on the content of the catalyst, and it may be included in the amount of catalyst depending on the composition of the curable polyorganosiloxane component.

[0091] In addition to the above components, the curable composition may additionally include additional additives, for example, pigments or dyes, dispersants, thixotropic agents, flame retardants, etc., if necessary.

[0092] The curable composition may be a one-component composition as described above, a main component or curing agent composition of a two-component composition, or a mixture of a main component and a curing agent composition of a two-component composition.

[0093] In the case of a mixture of a main component and a curing agent composition of a one-component or two-component composition, the curable composition may simultaneously include the aforementioned components.

[0094] In addition, when the curable composition is the main component of a two-component composition, the main component may include the alkenyl group-containing polyorganosiloxane component as the curable polyorganosiloxane component, and may additionally include the catalyst and filler components.

[0095] In addition, when the resin composition is a curing agent composition of a two-component composition, the curing agent composition may include the alkenyl group-containing polyorganosiloxane component and the silicon-bonded hydrogen-containing polyorganosiloxane component as curable polyorganosiloxane components, additionally include the filler component, and may not include a catalyst. In this case, not including a catalyst means substantially not including it and intentionally not adding it, and it may be said that it is substantially not included in cases where it is included in an amount of about 0.01 weight% or less, 0.001 weight% or less, 0.0001 weight% or less, or 0.00001 weight% or less relative to the total weight of the composition.

[0096] In each of the above cases, the specific types of polyorganosiloxane components, filler components, catalysts, etc., and their mixing ratios are as described above.

[0097] In one example, when the resin composition is a two-component curable composition, the resin composition comprises physically separated main component composition and curing agent composition, the main component composition comprises an alkenyl group-containing polyorganosiloxane component and a filler component, and the curing agent composition may comprise an alkenyl group-containing polyorganosiloxane component, a silicon-bonded hydrogen-containing polyorganosiloxane component and a filler component.

[0098] In such cases, the subject composition may include a catalyst, and the curing agent composition may not include a catalyst.

[0099] In one example, the ratio (Ak1 / Ak2) of the number of moles of alkenyl groups (Ak1) of the alkenyl group-containing polyorganosiloxane component of the main component of the two-component curable composition and the number of moles of alkenyl groups (Ak2) of the alkenyl group-containing polyorganosiloxane component of the curing agent composition may be in the range of 0.5 to 5. Specifically, the ratio (Ak1 / Ak2) may be 0.7 or more, 0.8 or more, 0.9 or more, 1.0 or more, 1.1 or more, or 1.2 or more, or 4 or less, 3.5 or less, 3 or less, 2.5 or less, 2 or less, or 1.5 or less.

[0100] In one example, the ratio (H / Ak) of the total number of moles of silicon-bonded hydrogen atoms (H) to the total number of moles of alkenyl groups (Ak) of the two-component curable composition may exceed 1. Specifically, the ratio of the total number of moles of silicon-bonded hydrogen atoms to the total number of moles of alkenyl groups may be 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more, 2 or more, 3 or more, 4 or more, or 5 or more. When the ratio of the moles of silicon-bonded hydrogen atoms to the moles of alkenyl groups is adjusted to the above range, there is an advantage that the two-component curable composition can be stored for a long time without surface treatment of the filler. Here, the ratio of the total number of moles of silicon-bonded hydrogen atoms to the total number of moles of alkenyl groups of the two-component curable composition may be the ratio of the total number of moles of silicon-bonded hydrogen atoms to the total number of moles of alkenyl groups of the main composition and the curing agent composition.

[0101] In the above case, the specific types of polyorganosiloxane components, filler components, catalysts, etc., and their mixing ratios are as described above.

[0103] In one example, the viscosity value of the two-component curable composition may be about 1,000,000 cP or less. The lower limit may be, for example, about 2,000 cP or more. As an example, the viscosity value of the two-component curable composition may be about 950,000 cP or less, 900,000 cP or less, or about 850,000 cP or less, and may be about 3,000 cP or more, 4,000 cP or more, or about 5,000 cP or more. When the range is satisfied, long-term storage stability of the composition is ensured, and appropriate processability can also be ensured.

[0104] The two-component curable composition of the present application may have physical properties suitable for the uses described below after curing.

[0105] In one example, the two-component curable composition may have a predetermined adhesive strength at room temperature after curing. Specifically, the adhesive strength to aluminum measured according to the ASTM D1002 standard is 3.8 kgf / cm² 2 Above, 4.0 kgf / cm² 2 Above, 4.2 kgf / cm² 2 Above, 4.4 kgf / cm² 2 Above, 4.6 kgf / cm² 2 Above, 4.8 kgf / cm² 2 Above, 5.0 kgf / cm² 2 Above, 5.5 kgf / cm² 2 Above, 6.0 kgf / cm² 2 ≥ or 6.5 kgf / cm² 2 It may be greater than. The above upper limit of adhesive strength is not specifically limited, for example, 10.0 kgf / cm² 2 Below, 9.0 kgf / cm² 2 ≤ or 8.0 kgf / cm² 2 The following may be possible. As described above, a two-component curable composition exhibiting excellent adhesion to metal can be effectively used in various applications requiring heat dissipation materials.

[0106] In one example, the two-component curable composition may have a predetermined hardness at room temperature after curing. In this case, it may be desirable for the cured layer of the composition to exhibit an appropriate hardness. For example, if the hardness of the cured layer is excessively high, the cured layer may have brittle characteristics, which can have a negative effect on reliability. Considering this, impact resistance and vibration resistance can be secured and product durability can be ensured by controlling the hardness of the cured layer. For example, the hardness of the cured layer in the Shore OO type may be 50 or higher, 55 or higher, 60 or higher, 65 or higher, or 70 or higher, and may be 90 or lower, 88 or lower, 86 or lower, 84 or lower, or 82 or lower. Hardness within the above range can be controlled by the content of the filler and curing agent in the two-component curable composition.

[0107] In one example, the two-component curable composition has a hardness (H0) immediately after preparation (0 day) and a hardness (H) when left at room temperature for a period of 15 days (15 days) or longer. 15 The ratio of ) (H0 / H 15 ) may be 0.6 or higher, 0.65 or higher, 0.7 or higher, 0.75 or higher, or 0.8 or higher. The above hardness (H0 and H 15 ) may be a shore OO type, and the above ratio (H0 / H) is based on the content of filler and curing agent in the two-component curable composition. 15 ) can be adjusted.

[0108] The two-component curable composition of the present application can be applied to various applications requiring a heat dissipation material, and the scope of such application is not particularly limited. For example, as a battery-related technology, the two-component curable composition can be applied as a heat dissipation material for battery modules or battery packs, or as a heat dissipation material for vehicle On-Board Chargers (OBCs). Accordingly, the present application also relates to a battery module, battery pack, or on-board charger (OBC) comprising the two-component curable composition or the cured product thereof as a heat dissipation material. The application location or method of the two-component curable composition or the cured product in the battery module, battery pack, or on-board charger is not particularly limited, and known methods may be applied. Furthermore, the two-component curable composition of the present application is not limited to the above applications and can be effectively applied to various applications requiring excellent heat dissipation characteristics, storage stability, and adhesion.

[0109] In another example relating to the present application, the present application may relate to electronic equipment or devices having a cured product of the two-component curable composition. The type of electronic equipment or device is not particularly limited, and examples may include an audio-video navigation (AVN) or an on-board charger (OBC) module for an electric vehicle, an LED module or IC chip, and a computer or mobile device including the same.

[0110] The cured product of the above two-component curable composition can dissipate heat within the equipment or device and provide durability against impact and insulation properties. Effects of the invention

[0111] The present application provides a curable composition that has a simple manufacturing process, reduced manufacturing costs, and ensures long-term storage stability. Brief explanation of the drawing

[0112] Figure 1 is a graph showing the change in hardness according to the storage period of the curable compositions of Examples 1 to 3 and Comparative Example 1. Specific details for implementing the invention

[0113] The present application will be specifically described through the following examples, but the scope of the present application is not limited by the following examples.

[0115] 1. Hardness

[0116] The main component composition and the curing agent composition prepared in the examples or comparative examples were each placed into a two-component cartridge, mixed in a 1:1 volume ratio, and cured into a film with a thickness of approximately 5 mm. Subsequently, the hardness of the film surface was measured according to ASTM D 2240. An ASKER Durometer was used for the hardness measurement. An initial hardness was measured by applying a load of approximately 1.5 kg to the surface of a flat sample, and the hardness was evaluated by confirming the stabilized measurement value after 15 seconds. Shore OO hardness was measured.

[0118] 2. Thermal conductivity

[0119] The main component composition and the curing agent composition prepared in the example or comparative example were each placed into a two-component cartridge and mixed in a 1:1 volume ratio, and after curing into a film with a thickness of about 5 mm, the thermal conductivity in the thickness direction of the film was measured. The thermal conductivity was measured using a Hot Disk measuring device according to the ISO 22007-2 standard, which measures temperature changes while heating a sensor in which the nickel wire has a double spiral structure.

[0121] 3. Viscosity

[0122] The viscosity of the main component, curing agent, or resin composition was measured using an Advanced Rheometic Expansion System (Brookfield, DV3T Rheometer, CPA-52Z spindle). The temperature conditions were set to room temperature (approx. 25°C) with a gap of 5 mm. Viscosity was measured while varying the shear rate from 0.1 / s to 10.0 / s. The viscosities listed below are values ​​at a shear rate of 1 / s.

[0124] 4. 1 H NMR analysis

[0125] Regarding polyorganosiloxane components 1 H NMR analysis was performed in a known manner. The analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer equipped with a triple resonance 5 mm probe. The polyorganosiloxane component to be analyzed was diluted to a concentration of approximately 10 mg / ml in an NMR measurement solvent (CDCl3), and the chemical shift was expressed in ppm.

[0127] 5. 29 Si NMR analysis

[0128] Regarding polyorganosiloxane components 29 Si NMR analysis was performed using a known method. 29 For Si NMR analysis, TMS (dilute tetramethylsilane in CDCl3) was used as the reference compound to represent chemical shifts.

[0130] 6. GPC(Gel Permeation Chromatograph)

[0131] The number-average molecular weight (Mn) and molecular weight distribution of the polyorganosiloxane components were measured using gel permeation chromatography (GPC). The polyorganosiloxane to be analyzed was placed in a 5 mL vial and diluted in tetrahydrofuran (THF) to a concentration of approximately 5 mg / mL. Subsequently, the standard sample for calibration and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) before measurement. The analysis program used was ChemStation by Agilent Technologies. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined by comparing the sample elution time with the calibration curve, and the molecular weight distribution (PDI) was calculated using the ratio (Mw / Mn). The GPC measurement conditions are as follows.

[0132] <GPC 측정 조건>

[0133] Device: Agilent Technologies 1200 series

[0134] Column: Used 2 PLgel mixed B units from Polymer Laboratories

[0135] Solvent: THF (tetrahydrofuran)

[0136] Column temperature: 40℃

[0137] Sample concentration: 5 mg / mL, 10 μL injection

[0138] Standard Sample: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

[0140] Example 1.

[0141] Preparation of the subject composition

[0142] 10g of a main part containing 7.92g of a polyorganosiloxane component (VP1000, DamiPolychem) having a viscosity of 1000cP and containing a polyorganosiloxane of the following chemical formula A, 1.98g of a polyorganosiloxane component (DSVP100, Double S Solution) having a viscosity of 100cP and containing a polyorganosiloxane of the following chemical formula B, and 0.1g of a platinum catalyst (1,3-divinyl-1,1,3,3-tetramethyl-disiloxane-platinum(0)-complex) was mixed with aluminum hydroxide having a D50 particle size of about 50 μm and aluminum hydroxide having a D50 particle size of about 1 μm in a weight ratio of 7:3. The above aluminum hydroxide mixed filler was included in an amount of 475 parts by weight per 100 parts by weight of a polyorganosiloxane component containing polyorganosiloxanes of chemical formulas A and B.

[0143] A polyorganosiloxane component containing the polyorganosiloxane of the above chemical formula A, measured in the manner described above 1 In H-NMR analysis, the area ratio of the Si-Vinyl peak to Si-CH3 (Si-CH3 / Si-Vinyl) was approximately 252, and based on this, the vinyl group content confirmed was approximately 0.107 mmol / g. For the polyorganosiloxane component containing the polyorganosiloxane of the above chemical formula B, measured in the manner described above 1 In H-NMR analysis, the area ratio of the Si-Vinyl peak to Si-CH3 (Si-CH3 / Si-Vinyl) was approximately 93, and based on this, the vinyl group content was confirmed to be approximately 0.29 mmol / g.

[0144] The number average molecular weight (Mn) measured by GPC of the polyorganosiloxane component containing the polyorganosiloxane of formula A was approximately 14,800 g / mol, the weight average molecular weight (Mw) was approximately 35,500 g / mol, and the molecular weight distribution (PDI=Mw / Mn) was approximately 2.40. The number average molecular weight (Mn) measured by GPC of the polyorganosiloxane component containing the polyorganosiloxane of formula B was approximately 7,020 g / mol, the weight average molecular weight (Mw) was approximately 13,700 g / mol, and the molecular weight distribution (PDI=Mw / Mn) was approximately 1.95.

[0145] The above ingredients were added to a paste mixer and mixed for about 3 minutes at 600 rpm and 500 rpm to disperse them, after which the heat generated was checked, and the main composition was prepared by degassing for 4 minutes at 600 rpm and 200 rpm under vacuum.

[0146] [Chemical Formula A]

[0147]

[0148] In chemical formula A, m is a number of about 250.

[0149] [Chemical Formula B]

[0150]

[0151] In chemical formula B, n is a number of about 91.

[0153] Preparation of a curing agent composition

[0154] 10g of a curing agent part containing 6.12g of a polyorganosiloxane component containing the polyorganosiloxane of the above chemical formula A, 1.53g of a polyorganosiloxane component containing the above chemical formula B, 0.35g of a polyorganosiloxane component containing the polyorganosiloxane of the following chemical formula C (XL11, AB Specialty Silicones), and 2g of a polyorganosiloxane component containing the polyorganosiloxane of the following chemical formula D (CE4, AB Specialty Silicones) was mixed with aluminum hydroxide having a D50 particle size of about 50 μm and aluminum hydroxide having a D50 particle size of about 1 μm in a weight ratio of 7:3. The above aluminum hydroxide mixed filler is included in an amount of 614 parts by weight per 100 parts by weight of a polyorganosiloxane component containing polyorganosiloxanes of formulas A and B, and in an amount of 2000 parts by weight per 100 parts by weight of a polyorganosiloxane component containing polyorganosiloxanes of formulas C and D.

[0155] The above performed on a polyorganosiloxane component comprising a polyorganosiloxane of chemical formula C 29 As a result of performing Si NMR analysis, the M units at both ends ((CH3)3SiO2) in the structure of chemical formula C 1 / 2 The molar ratio of the unit is approximately 4.3 mol%, and the hydrogen-free D unit (CH3)2SiO 2 / 2 The molar ratio of the unit is approximately 68.8 mol%, and the hydrogen-containing D unit (H(CH3)SiO2) 2 / 2 The molar ratio of (unit) was approximately 26.9 mol%. Also, 1 The ratio of the Si-H peak to the Si-CH3 peak (Si-CH3 / Si-H) confirmed by H NMR analysis was approximately 19.2, and the silicon-bonded hydrogen content confirmed through this was approximately 4.14 mmol / g.

[0156] In addition, performed on a polyorganosiloxane component containing a polyorganosiloxane of chemical formula D 1The ratio of the Si-H peak to the Si-CH3 peak (Si-CH3 / Si-H) confirmed by H NMR analysis was approximately 34.2, and the silicon-bonded hydrogen content confirmed through this was approximately 2.9 mmol / g.

[0157] The above ingredients were added to a paste mixer and mixed for about 3 minutes at 600 rpm and 500 rpm to disperse them, after which the heat generated was checked, and a curing agent composition was prepared by degassing for 4 minutes at 600 rpm and 200 rpm under vacuum.

[0158] [Chemical Formula C]

[0159]

[0160] In the chemical formula C, p is a number of about 32, and q is a number of about 13.

[0161] [Chemical Formula D]

[0162]

[0163] In the chemical formula D, n is a number of about 9.

[0165] Aluminum hydroxide was included in each of the above-mentioned main composition and curing agent composition at a volume of 65%, and a curable composition was prepared by mixing such that the molar ratio (B / A) of the alkenyl group (A) of the main composition and curing agent composition and the silicon-bonded hydrogen (B) of the curing agent composition was 2.88.

[0167] Example 2.

[0168] Preparation of the subject composition

[0169] The subject composition prepared in Example 1 above was used.

[0171] Preparation of a curing agent composition

[0172] A curing agent composition was prepared in the same manner as in Example 1, except that a curing agent part was prepared containing 6.52 g of a polyorganosiloxane component containing the polyorganosiloxane of Formula A, 1.63 g of a polyorganosiloxane component containing the polyorganosiloxane of Formula B, 0.35 g of a polyorganosiloxane component containing the polyorganosiloxane of Formula C (XL11, AB Specialty Silicones), and 1.5 g of a polyorganosiloxane component containing the polyorganosiloxane of Formula D (CE4, AB Specialty Silicones), which were used when preparing the curing agent composition in Example 1.

[0174] Aluminum hydroxide was included in each of the above-mentioned main composition and curing agent composition at a volume of 65%, and a curable composition was prepared by mixing such that the molar ratio (B / A) of the alkenyl group (A) of the main composition and curing agent composition and the silicon-bonded hydrogen (B) of the curing agent composition was 1.72.

[0176] Example 3.

[0177] Preparation of the subject composition

[0178] 10g of a main part containing 9.98g of a polyorganosiloxane component (VP1000, Damipolychem) containing the polyorganosiloxane of Formula A used when preparing the main composition in Example 1 above and 0.02g of a platinum catalyst (1,3-divinyl-1,1,3,3-tetramethyl-disiloxane-platinum(0)-complex) was mixed with aluminum hydroxide having a D50 particle size of about 50 μm and aluminum hydroxide having a D50 particle size of about 1 μm in a weight ratio of 7:3. The aluminum hydroxide mixed filler was included in an amount of 301 parts by weight relative to 100 parts by weight of the polyorganosiloxane component containing the polyorganosiloxanes of Formulas A and B.

[0180] Preparation of a curing agent composition

[0181] In the above Example 1, 10g of a curing agent part containing 5g of a polyorganosiloxane component containing the polyorganosiloxane of Formula A used when preparing the main composition, 1.67g of a polyorganosiloxane component containing the polyorganosiloxane of Formula C (XL11, AB Specialty Silicones), and 3.33g of a polyorganosiloxane component containing the polyorganosiloxane of Formula D (CE4, AB Specialty Silicones) was mixed with aluminum hydroxide having a D50 particle size of about 50 μm and aluminum hydroxide having a D50 particle size of about 1 μm in a weight ratio of 7:3. The aluminum hydroxide mixed filler was included in an amount of 600 parts by weight relative to 100 parts by weight of the polyorganosiloxane component containing the polyorganosiloxanes of Formulas C and D.

[0182] The above ingredients were added to a paste mixer and mixed for about 3 minutes at 600 rpm and 500 rpm to disperse them, after which the heat generated was checked, and a curing agent composition was prepared by degassing for 4 minutes at 600 rpm and 200 rpm under vacuum.

[0184] Aluminum hydroxide was included in each of the above-mentioned main composition and curing agent composition at a volume of 54%, and a curable composition was prepared by mixing such that the molar ratio (B / A) of the alkenyl group (A) of the main composition and curing agent composition and the silicon-bonded hydrogen (B) of the curing agent composition was 3.81.

[0186] Comparative Example 1

[0187] Preparation of the subject composition

[0188] 8.18 g of a polyorganosiloxane component (VP1000, DamiPolychem) containing a polyorganosiloxane of the following chemical formula A with a viscosity of 1000 cP, 1.67 g of a polyorganosiloxane component (DSVP100, Double S Solution) containing a polyorganosiloxane of the following chemical formula B with a viscosity of 100 cP, and 0.15 g of a platinum catalyst (1,3-divinyl-1,1,3,3-tetramethyl-disiloxane-platinum(0)-complex) were mixed with aluminum hydroxide having a D50 particle size of about 50 μm and aluminum hydroxide having a D50 particle size of about 1 μm in a weight ratio of 7:3. The above aluminum hydroxide mixed filler was included in an amount of 477 parts by weight per 100 parts by weight of a polyorganosiloxane component containing polyorganosiloxanes of chemical formulas A and B.

[0189] The above ingredients were added to a paste mixer and mixed for about 3 minutes at 600 rpm and 500 rpm to disperse them, after which the heat generated was checked, and the main composition was prepared by degassing for 4 minutes at 600 rpm and 200 rpm under vacuum.

[0190] [Chemical Formula A]

[0191]

[0192] In chemical formula A, m is a number of about 250.

[0193] [Chemical Formula B]

[0194]

[0195] In chemical formula B, n is a number of about 91.

[0196] Preparation of a curing agent composition

[0197] 7.96 g of a polyorganosiloxane component containing the polyorganosiloxane of Formula A and 1.67 g of a polyorganosiloxane component containing the polyorganosiloxane of Formula B were mixed with 10 g of a curing agent part containing 0.37 g of a polyorganosiloxane component (FD5020, DamiPolychem) containing the polyorganosiloxane of Formula C, such that the ratio of aluminum hydroxide with a D50 particle size of about 50 μm to aluminum hydroxide with a D50 particle size of about 1 μm was 7:3 by weight. The aluminum hydroxide mixed filler was included in an amount of 488 parts by weight relative to 100 parts by weight of the polyorganosiloxane component containing the polyorganosiloxanes of Formulas A and B, and in an amount of 12,703 parts by weight relative to 100 parts by weight of the polyorganosiloxane component containing the polyorganosiloxane of Formula C.

[0198] The above ingredients were added to a paste mixer and mixed for about 3 minutes at 600 rpm and 500 rpm to disperse them, after which the heat generated was checked, and a curing agent composition was prepared by degassing for 4 minutes at 600 rpm and 200 rpm under vacuum.

[0199] [Chemical Formula C]

[0200]

[0201] In the chemical formula C, p is a number of about 39, and q is a number of about 8.

[0203] Aluminum hydroxide was included in each of the above-mentioned main composition and curing agent composition at a volume of 65%, and a curable composition was prepared by mixing such that the molar ratio (B / A) of the alkenyl group (A) of the main composition and curing agent composition and the silicon-bonded hydrogen (B) of the curing agent composition was 0.4.

[0205] To evaluate storage stability, the thermal conductivity and hardness of the curable composition of Comparative Example 1 were evaluated immediately after preparation (0d), after 3 days (3d), after 9 days (9d), and after 15 days (15d), and are summarized in Table 1 below. In addition, the thermal conductivity and hardness of the curable compositions of Examples 1 to 3 immediately after preparation and after time has elapsed are summarized in Table 1 below.

[0206] division Storage period of curable composition (25℃) Thermal conductivity (W / mK) Longitude (shore 00) Comparative Example 1 0d 1.86 66 3d 1.82 50 9d 1.87 46 15d 1.85 39 Example 1 0d 1.87 74 4d 1.89 69 10d 1.84 63 17d 1.87 60 Example 2 0d 1.88 81 5d 1.90 79 12d - 79 19d 1.87 75 Example 3 0d 1.22 78 7d 1.26 82 14d 1.24 74 21d 1.17 78

[0207] Referring to Figure 1 and Table 1, the hardness of the curable composition of Comparative Example 1 decreased by 20 or more within 10 days of preparation, whereas the curable compositions of Examples 1 to 3 exhibited appropriate thermal conductivity and a small decrease in hardness over time, thus ensuring storage stability.

Claims

Claim 1 A two-component curable composition comprising a main component composition and a curing agent composition, wherein the main component composition comprises an alkenyl group-containing polyorganosiloxane component and a filler component comprising a filler having hydroxyl groups on its surface, and the curing agent composition comprises an alkenyl group-containing polyorganosiloxane component, a silicon-bonded hydrogen-containing polyorganosiloxane component, and a filler component having hydroxyl groups on its surface, wherein the volume ratio of the filler component is 50 to 75 volume%, the alkenyl group content of the alkenyl group-containing polyorganosiloxane component is within the range of 0.05 to 5 mmol / g, and the ratio (H / Ak) of the molar number of silicon-bonded hydrogens (H) of the silicon-bonded hydrogen-containing polyorganosiloxane component to the molar number of alkenyl groups (Ak) of the alkenyl group-containing polyorganosiloxane component is within the range of 2 to 10, and the silicon-bonded hydrogen content of the curing agent composition A two-component curable composition comprising: a first polyorganosiloxane component having a compound of the following chemical formula 2; and a second polyorganosiloxane component having a compound of the following chemical formula 3, wherein the silicon-bonded hydrogen content of the first polyorganosiloxane component is in the range of 2 to 10 mmol / g and the silicon-bonded hydrogen content of the second polyorganosiloxane component is in the range of 2 to 6 mmol / g, and the ratio (H / Ak) of the molar number of alkenyl groups (Ak) contained in the alkenyl group-containing polyorganosiloxane component of the main component and curing agent composition and the molar number of silicon-bonded hydrogens (H) contained in the silicon-bonded hydrogen-containing polyorganosiloxane component of the curing agent composition is 1.5 or higher: [Chemical Formula 2] In Chemical Formula 2, R3 is an alkyl group, m is a number within the range of 7 to 25, [Chemical Formula 3] In Chemical Formula 3, R4 is an alkyl group, p is a number in the range of 20 to 60, and q is a number in the range of 3 to 20. Claim 2 A two-component curable composition according to claim 1, wherein the ratio (Ak1 / Ak2) of the number of moles of alkenyl groups (Ak1) of the alkenyl group-containing polyorganosiloxane component of the main composition and the number of moles of alkenyl groups (Ak2) of the alkenyl group-containing polyorganosiloxane component of the curing agent composition is within the range of 0.5 to 5. Claim 3 In claim 1, the subject composition is a two-component curable composition further comprising a catalyst. Claim 4 delete Claim 5 In claim 1, the alkenyl group-containing polyorganosiloxane component of the curing agent composition is a two-component curable composition having a polyorganosiloxane represented by the following chemical formula 1: [Chemical Formula 1] In Chemical Formula 1, R5 is an alkenyl group, R6 is an alkyl group, and n is a number in the range of 30 to 300. Claim 6 delete Claim 7 delete Claim 8 A two-component curable composition according to claim 1, wherein the ratio (H1 / H2) of the molar number of silicon-bonded hydrogens (H2) of the second polyorganosiloxane component to the molar number of silicon-bonded hydrogens (H1) of the first polyorganosiloxane component is within the range of 0.5 to 5. Claim 9 A two-component curable composition in which the filler of the curing agent composition is an inorganic hydroxide. Claim 10 In claim 9, the filler component of the curing agent composition comprises a first inorganic hydroxide having an average particle size of 20 μm or more and a second inorganic hydroxide having an average particle size of 10 μm or less, in a two-component curable composition. Claim 11 A two-component curable composition according to claim 10, wherein the ratio (D1 / D2) of the average particle size (D1) of the first inorganic hydroxide and the average particle size (D2) of the second inorganic hydroxide is within the range of 2 to 200. Claim 12 A two-component curable composition according to claim 10, wherein the ratio (W1 / W2) of the weight of the first inorganic hydroxide (W1) and the weight of the second inorganic hydroxide (W2) is within the range of 0.5 to 10. Claim 13 A two-component curable composition according to claim 1, wherein the ratio of the filler component of the curing agent composition is within the range of 300 to 900 parts by weight relative to 100 parts by weight of the alkenyl group-containing polyorganosiloxane component in the curing agent composition. Claim 14 A two-component curable composition according to claim 1, wherein the ratio of the filler component of the curing agent composition is within the range of 1,000 to 30,000 parts by weight per 100 parts by weight of the silicon-bonded hydrogen-containing polyorganosiloxane component in the curing agent composition. Claim 15 In claim 1, the curing agent composition is a two-component curable composition that does not contain a catalyst. Claim 16 A polyorganosiloxane component containing an alkenyl group; a polyorganosiloxane component containing a silicon-bonded hydrogen; and a filler component having a filler having a hydroxyl group on its surface, wherein the volume ratio of the filler component is 50 to 75 volume%, the alkenyl group content of the polyorganosiloxane component containing an alkenyl group is within the range of 0.05 to 5 mmol / g, and the ratio (H / Ak) of the molar number of silicon-bonded hydrogens (H) of the polyorganosiloxane component containing silicon-bonded hydrogens to the molar number of alkenyl groups (Ak) of the polyorganosiloxane component containing an alkenyl group is within the range of 2 to 10, and the silicon-bonded hydrogen-bonded polyorganosiloxane component is a first polyorganosiloxane component having a compound of the following chemical formula 2; A curable composition comprising a second polyorganosiloxane component having a compound of the following chemical formula 3, wherein the silicon-bonded hydrogen content of the first polyorganosiloxane component is in the range of 2 to 10 mmol / g and the silicon-bonded hydrogen content of the second polyorganosiloxane component is in the range of 2 to 6 mmol / g: [Chemical Formula 2] In Chemical Formula 2, R3 is an alkyl group, m is a number within the range of 7 to 25, [Chemical Formula 3] In Chemical Formula 3, R4 is an alkyl group, p is a number in the range of 20 to 60, and q is a number in the range of 3 to 20. Claim 17 In claim 16, the alkenyl group-containing polyorganosiloxane component is a curable composition having a polyorganosiloxane represented by the following chemical formula 1: [Chemical Formula 1] In Chemical Formula 1, R5 is an alkenyl group, R6 is an alkyl group, and n is a number in the range of 30 to 300. Claim 18 delete Claim 19 delete Claim 20 A curable composition according to claim 16, wherein the ratio (H1 / H2) of the molar number of silicon-bonded hydrogens (H2) of the second polyorganosiloxane component to the molar number of silicon-bonded hydrogens (H1) of the first polyorganosiloxane component is within the range of 0.5 to 5. Claim 21 In claim 16, the filler is a curable composition in which the filler is an inorganic hydroxide. Claim 22 In claim 21, the filler component comprises a first inorganic hydroxide having an average particle size of 20 μm or more and a second inorganic hydroxide having an average particle size of 10 μm or less, forming a curable composition. Claim 23 A curable composition according to claim 22, wherein the ratio (D1 / D2) of the average particle size (D1) of the first inorganic hydroxide and the average particle size (D2) of the second inorganic hydroxide is within the range of 2 to 200. Claim 24 A curable composition according to claim 22, wherein the ratio (W1 / W2) of the weight of the first inorganic hydroxide (W1) and the weight of the second inorganic hydroxide (W2) is within the range of 0.5 to 10. Claim 25 A curable composition according to claim 16, wherein the ratio of the filler component is within the range of 200 to 900 parts by weight per 100 parts by weight of the alkenyl group-containing polyorganosiloxane component. Claim 26 A curable composition according to claim 16, wherein the ratio of the filler component is within the range of 1,000 to 30,000 parts by weight per 100 parts by weight of the silicon-bonded hydrogen-containing polyorganosiloxane component. Claim 27 In claim 16, a curable composition that does not contain a catalyst.

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