Curable composition and two-component curable composition

Abstract

This application provides a curable composition with excellent storage stability due to its physical properties, such as viscosity or hardness, remaining unchanged during storage, as well as a two-component curable composition comprising such a curable composition. Furthermore, this application provides a curable composition with excellent storage stability without the use of separate additives or any surface-treatment processes for thermally conductive fillers, as well as a two-component curable composition comprising such a curable composition.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0127591 filed on September 29, 2020 and Korean Patent Application No. 10-2021-0124663 filed on September 17, 2021, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

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

[0005] Heat dissipation materials are used in various fields. Taking vehicles as an example, heat dissipation materials can be used to handle the heat generated by the rechargeable and dischargeable battery modules built into electric vehicles, the on-board charger (OBC) that charges the battery, etc., and heat dissipation materials are also suitable for components that consume high power and generate a lot of heat, such as LED modules, thereby increasing the life of the LED modules.

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

[0007] However, if an inorganic hydroxide filler without surface treatment is used, the highly active inorganic hydroxide filler reacts with the curing agent in the resin composition, and the viscosity and hardness of the resin composition or the cured product vary over time and deviate from the designed range, thereby possibly causing a problem of deterioration in long-term storage stability.

[0008] To solve this problem, there is a method of surface-treating an inorganic hydroxide filler to mix it with a siloxane resin composition, but this method requires a lot of time and money, and therefore a method is also needed to ensure long-term storage stability of the resin composition without surface-treating the filler. Summary of the invention

[0009] Technical issues

[0010] The present application aims to provide a curable composition having excellent storage stability due to no change in physical properties such as viscosity or hardness during storage, and a two-component curable composition including the curable composition.

[0011] Furthermore, the present application aims to provide a curable composition having excellent storage stability of a thermally conductive filler without using a separate additive or without using any surface treatment process, and a two-component curable composition comprising the curable composition.

[0012] Technical Solution

[0013] Among the physical properties mentioned in this specification, the physical properties whose physical properties are affected by measuring temperature are the physical properties measured at room temperature unless otherwise specified.

[0014] In this specification, the term room temperature is a natural temperature without heating and cooling, and refers to, for example, any temperature in the range of about 10° C. to 30° C., such as a temperature of about 15° C., about 18° C., about 20° C., about 23° C., or about 25° C. In addition, in this specification, unless otherwise specified, the temperature unit is ° C.

[0015] In the present specification, the term alkenyl group may refer to a linear, branched 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 otherwise specified.

[0016] In the present specification, the term alkyl or alkoxy may refer to a linear, branched or cyclic alkyl 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 otherwise specified.

[0017] In this specification, the term aromatic group may refer to a monovalent residue from a compound comprising a benzene structure, a compound comprising a structure in which two or more benzenes are connected by a linking group, or a compound comprising a structure in which two benzenes are condensed or bonded, each of which shares one or two carbon atoms, or a derivative of any of the above compounds, unless otherwise specified. Within the scope of the aromatic group mentioned herein, a functional group referred to as an aromatic alkyl or an aromatic alkyl group and commonly referred to as an aromatic group may also be included. The aromatic group may, for example, be an aromatic group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. The aromatic group may, for example, be phenyl, dichlorophenyl, chlorophenyl, phenethyl, phenylpropyl, benzyl, tolyl, xylyl, or naphthyl, etc.

[0018] The alkenyl, alkoxy, alkyl or aromatic group may be optionally substituted with one or more substituents. In this case, the substituent may be halogen such as chlorine or fluorine, epoxy such as glycidyl, epoxyalkyl, glycidyl ether oxide or alicyclic epoxy, acryloyl, methacryloyl, isocyanate, thiol or monovalent hydrocarbon group, but is not limited thereto.

[0019] In the present specification, the term M unit may refer to a so-called monofunctional siloxane unit, which may generally be composed of (R3SiO 1 / 2 ) represents; the term D unit may refer to a so-called difunctional siloxane unit, which can generally be represented by (R2SiO 2 / 2 ) represents; the term T unit may refer to a so-called trifunctional siloxane unit, which can generally be represented by (RSiO 3 / 2 ) represents; and the term Q unit may refer to a so-called tetrafunctional siloxane unit, which can generally be composed of (SiO 4 / 2 In the formula of each siloxane unit, each R is a functional group bonded to silicon (Si), which may be, for example, hydrogen, an alkyl group, an alkenyl group, an aromatic group, an alkoxy group, or an epoxy group.

[0020] The curable composition of the present application may include an alkenyl-containing polyorganosiloxane component, a silicon-bonded hydrogen-containing polyorganosiloxane component, and a filler component, wherein the filler component has a filler having a hydroxyl group on its surface. The curable composition of the present application is cured by the reaction (addition reaction (hydrosilylation reaction product)) of the alkenyl group of the alkenyl-containing polyorganosiloxane component and the hydrogen of the silicon-bonded hydrogen-containing polyorganosiloxane component.

[0021] In one example, the curable composition can be a one-component resin composition, a main composition of a two-component resin composition, a curing agent composition of a two-component resin composition, or a mixture of a main composition and a curing agent composition of a two-component resin composition. The one-component resin composition is a resin composition in which the curable component is stored in a mixed state, and the two-component resin composition is a resin composition in which the curable component is separated into a physically separated main composition and a curing agent composition and stored. In the case of a two-component resin composition, the main composition and the curing agent composition are mixed under conditions where curing can occur during use.

[0022] In the present specification, the term polyorganosiloxane component may be a mixture of polyorganosiloxanes and / or a mixture of polyorganosiloxane and siloxane monomers. In a more specific example, the polyorganosiloxane component may be a product obtained by polymerization to obtain a particularly desired polyorganosiloxane or a mixture of two or more products of the polymerization reaction.

[0023] As the alkenyl group-containing polyorganosiloxane component in the curable composition, known polyorganosiloxane components may be used without any particular limitation. In one example, as the polyorganosiloxane component, a polyorganosiloxane component including a linear polyorganosiloxane may be used.

[0024] The linear polyorganosiloxane is a known polyorganosiloxane having a structure in which both ends of a chain structure composed of D units are capped with M units.

[0025] Linear polyorganosiloxane is a polyorganosiloxane having a structure in which both ends of a chain structure composed of D units are capped with M units.

[0026] In the above structure, various types of units can be used as D units. For example, as D units, units selected from so-called dialkylsiloxane units (bifunctional siloxane units, wherein R2SiO 2 / 2 The two R in the structure are alkyl), diaryl siloxane unit (bifunctional siloxane unit, in which R2SiO 2 / 2 The two R in the structure are aromatic), diene siloxane unit (bifunctional siloxane unit, in which R2SiO 2 / 2 The two R in the structure are alkenyl), alkyl aromatic siloxane unit (bifunctional siloxane unit, wherein R2SiO 2 / 2 structural units, one R is an alkyl group and the other R is an aromatic group), alkyl alkenyl siloxane units (bifunctional siloxane units, wherein R2SiO 2 / 2 In the structure, one R is an alkyl group and the other R is an alkenyl group) and an aromatic alkenyl siloxane unit (a bifunctional siloxane unit in which R2SiO 2 / 2 In the structure, one R is an alkenyl group and the other R is an aromatic group).

[0027] Suitable D units can be exemplified by dialkylsiloxane units (difunctional siloxane units, wherein R2SiO 2 / 2 The two R in the structure are alkyl) and / or alkyl alkenyl siloxane units (bifunctional siloxane units, wherein R2SiO 2 / 2 In the structure, one R is an alkyl group and the other R is an alkenyl group).

[0028] In the linear polyorganosiloxane structure, the M units at both ends of the chain structure composed of D units can be exemplified by, for example, alkenyl dialkyl siloxane units (monofunctional siloxane units, wherein R3SiO 1 / 2 In the structure, one R is an alkenyl group and the other two are alkyl groups) and / or trialkylsiloxane units (monofunctional siloxane units, wherein R3SiO 1 / 2 In the structure, all R are alkyl groups) etc. For example, in the case of a structure having alkenyl groups at both ends, an alkenyldialkylsiloxane unit can be used as the M unit.

[0029] In one example, as the polyorganosiloxane having an alkenyl group, the polyorganosiloxane of the D unit of the main chain structure of the linear polyorganosiloxane is a dialkylsiloxane unit (a bifunctional siloxane unit in which R2SiO 2 / 2 In the structure, both R are alkyl) and / or alkyl alkenyl siloxane units (bifunctional siloxane units, wherein R2SiO2 / 2 In the structure, one R is an alkyl group and the other R is an alkenyl group), and the M units at both ends can use alkenyl dialkyl siloxane units (monofunctional siloxane units, in which R3SiO 1 / 2 In the structure, one R is an alkenyl group and the other two are alkyl groups).

[0030] When two or more D units are used as the D units of the main chain, the main chain shape may be that of a random copolymer, a block copolymer, or a gradient copolymer.

[0031] In one example, as the polyorganosiloxane component, a component represented by the following average unit formula A may be used.

[0032] The term average unit formula represents the unit formula of the molar ratio 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 has been converted to 1.

[0033] [Average unit formula A]

[0034] (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

[0035] In the average unit formula A, R 1 is alkenyl, R 2 is an alkyl group or an aromatic 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 a number in the range of 0 to 10.

[0036] In the average unit formula A, in another example, (a+b) may be greater than 0.007, or greater than 0.009, or may also be about 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 about 0.015 or less.

[0037] In the average unit formula A, in another example, (c+d) may be greater than 0.75, greater than 0.8, greater than 0.85, greater than 0.9, or greater than 0.95, or may also be less than 0.997, less than 0.995, less than 0.993, or less than 0.991.

[0038] In the average unit formula A, in another example, b / a can be about 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, or can be 0.

[0039] In the average unit formula A, in another example, c / d can be about 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, or can be 0.

[0040] In one example, the alkenyl group-containing polyorganosiloxane component may include a polyorganosiloxane represented by Formula 1 below.

[0041] [Formula 1]

[0042]

[0043] In Formula 1, R5 is an alkenyl group, R6 is an alkyl group or an aromatic group, and n is a number ranging from 30 to 300. In Formula 1, in another example, n can be 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, 110 or less, or about 100 or less.

[0044] In the above definition of Formula 1, specific types of alkenyl, alkyl, aromatic and the like are the same as those described in the technical solution introduction of this specification.

[0045] The alkenyl-containing polyorganosiloxane component may contain alkenyl groups in an amount of about 0.05 mmol / g to 5 mmol / g. In another example, the ratio of alkenyl groups may be about 0.1 mmol / g or more, 0.15 mmol / g or more, 0.2 mmol / g or more, or may be about 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 about 0.3 mmol / g or less. The above ratio is a value obtained by calculating the alkenyl ratio of the alkenyl-containing polyorganosiloxane component in the liquid curing agent composition without the filler component.

[0046] The ratio of the alkenyl group may be varied depending on the specific use of the curable composition, and when it satisfies the specified range, a desired viscosity can be ensured when mixed with a filler component.

[0047] For example, when the curable composition is a curing agent composition of a two-component curable composition, the proportion of the alkenyl group may also be in the range of about 0.1 mmol / g or more, 0.15 mmol / g or more, 0.2 mmol / g or more, or 0.25 mmol / g or less, 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.

[0048] In another example, when the curable composition is a mixture of a main composition of a two-component curable composition and a curing agent composition or a one-component curable composition, the alkenyl ratio within the above range may be further adjusted within the range of 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.

[0049] The alkenyl content and silicon-bonded hydrogen content of the polyorganosiloxane component mentioned in this specification are described in the examples. 1 H NMR and / or 29 The values ​​obtained by Si NMR analysis, the examples are described below for the polyorganosiloxane component. This method is different from the values ​​theoretically obtained by the chemical formula of the polyorganosiloxane contained in the polyorganosiloxane component. That is, various types of polyorganosiloxanes belonging to the same category of chemical formula but having different detailed structures may exist within the polyorganosiloxane component (for example, in the structure of Formula 1 above, there may be multiple polyorganosiloxanes with different n values), so the exact ratio between the curable functional groups (the ratio of alkenyl groups and silicon-bonded hydrogen) cannot be identified in this way.

[0050] This ratio plays an important role in ensuring the required storage stability (suppression of changes in viscosity and hardness over time) and thixotropy, which should be based on 1 H NMR and / or 29 The results of Si NMR analysis were used to determine the

[0051] In one example, the number average molecular weight (Mn) of the polyorganosiloxane having alkenyl groups may be in the range of 2500 g / mol to 20000 g / mol. In another example, the number average molecular weight (Mn) of the polyorganosiloxane having alkenyl groups 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 may be 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 about 14000 g / mol or less.

[0052] In addition, as the polyorganosiloxane component containing silicon-bonded hydrogen in the curable composition, known materials can be used without particular limitation. For example, as the polyorganosiloxane component, a linear polyorganosiloxane, that is, a polyorganosiloxane having a structure in which both ends of a straight chain structure composed of D units are capped by M units, can be used.

[0053] In the above structure, various types of units can be used as D units. For example, as D units, units selected from so-called dialkylsiloxane units (bifunctional siloxane units, wherein R2SiO 2 / 2 The two R in the structure are alkyl), diaryl siloxane unit (bifunctional siloxane unit, in which R2SiO 2 / 2 The two R in the structure are aromatic), dihydrogen siloxane unit (bifunctional siloxane unit, in which R2SiO 2 / 2 The two R in the structure are hydrogen), alkyl aromatic siloxane unit (bifunctional siloxane, in which R2SiO 2 / 2 In the structure, one R is an alkyl group and the other R is an aromatic group), alkyl hydrogen siloxane units (bifunctional siloxane units, in which R2SiO 2 / 2 In the structure, one R is an alkyl group and the other R is hydrogen) and aromatic hydrogen siloxane units (bifunctional siloxane units, in which R2SiO 2 / 2 The invention also provides at least one unit in which one R is hydrogen and the other R is an aromatic group.

[0054] Suitable D units can be exemplified. Among the aforementioned units, dialkylsiloxane units (bifunctional siloxane units, wherein R2SiO 2 / 2 The two R in the structure are alkyl) and / or alkyl hydrogen siloxane units (bifunctional siloxane units, wherein R2SiO 2 / 2 In the structure, one R is an alkyl group and the other R is hydrogen).

[0055] In the structure of the linear polyorganosiloxane, the M units at both ends of the straight chain structure composed of D units can be exemplified by hydrogen dialkylsiloxane units (monofunctional siloxane units, wherein R3SiO 1 / 2 In the structure, one R is hydrogen and the other two are alkyl) and / or trialkylsiloxane units (monofunctional siloxane units, wherein R3SiO 1 / 2 All R in the structure are alkyl), etc. For example, in the case of a structure where both ends are terminated with silicon-bonded hydrogen, a hydrogen dialkylsiloxane unit can be used as the M unit.

[0056] In one example, as the polyorganosiloxane component containing silicon-bonded hydrogen, a component represented by the following average unit formula B can be used.

[0057] [Average unit formula B]

[0058] (HR 3 2SiO 1 / 2 ) a (R 3 3SiO 1 / 2 ) b (R 3 2SiO 2 / 2 ) c (HR 3 SiO 2 / 2 ) d

[0059] In the average unit formula B, R 3 It can be an alkyl group or an aromatic group, a+b+c+d can be 1, a can be a number in the range of 0.001 to 0.2, b can be a number in the range of 0.01 to 0.8, c can be a number in the range of 0.01 to 0.7, and d can be a number in the range of 0.001 to 0.4.

[0060] In another example, a may be in 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 may also be in the range of 0.15 or less, or 0.1 or less.

[0061] In another example, b may be greater than 0.05, greater than 0.1, greater than 0.15, greater than 0.2, greater than 0.25, greater than 0.3, greater than 0.35, or greater than 0.4, or may be less than 0.7, less than 0.6, less than 0.5, or less than 0.45.

[0062] In another example, c can be a number in the range of greater than 0.05, greater than 0.1, greater than 0.15, greater than 0.2, greater than 0.25, or greater than 0.3, or can also be a number in the range of less than 0.65, less than 0.6, less than 0.55, less than 0.5, less than 0.45, less than 0.4, or less than 0.35.

[0063] In another example, d may be in 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 in 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 including a polyorganosiloxane of Formula 2 below and a second polyorganosiloxane component including a polyorganosiloxane of Formula 3.

[0064] [Formula 2]

[0065]

[0066] In Formula 2, R3 is an alkyl group or an aromatic group, and m is a number in 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 may be about 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 in another example.

[0067] [Formula 3]

[0068]

[0069] In Formula 3, R4 is an alkyl group or an aromatic group, p is a number in the range of 20 to 60, and q is a number in the range of 3 to 20. In 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 may be about 55 or less, 50 or less, 45 or less, or 40 or less. In addition, in Formula 3, q ​​may be 4 or more, 6 or more, 7.5 or more, 9 or more, or 11 or more, or may be about 18 or less, 17 or less, 16 or less, 15 or less, or 14 or less, in another example.

[0070] The specific types of the alkyl and aromatic groups in Formula 2 or Formula 3 are the same as those described in the introduction to the technical solution of this specification.

[0071] The mole number of silicon-bonded hydrogen contained in the first polyorganosiloxane component may be 0.5 mmol / g to 10 mmol / g. In another example, the first polyorganosiloxane component may contain the 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 in an amount of 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.

[0072] The molar amount of silicon-bonded hydrogen contained in the second polyorganosiloxane component may be 0.5 mmol / g to 6 mmol / g. In another example, the second polyorganosiloxane component may contain the 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 in an amount of 5.5 mmol / g or less, 5 mmol / g or less, or 4.5 mmol / g or less.

[0073] In one example, when the polyorganosiloxane component containing silicon-bonded hydrogen includes: a first polyorganosiloxane component; and a second polyorganosiloxane component, the ratio (H1 / H2) of the number of moles of silicon-bonded hydrogen in the first polyorganosiloxane component (H1) to the number of moles of silicon-bonded hydrogen in the second polyorganosiloxane component (H2) can be in the range of 0.5 to 10.

[0074] In another example, the ratio (H1 / H2) can be greater than 1, greater than 1.5, greater than 2, greater than 2.5, greater than 3, greater than 3.5, or greater than 4, or can also be less than 9, less than 8, less than 7, less than 6, less than 5, or less than 4.5.

[0075] In the curable composition, the ratio (H / Ak) of the mole number of silicon-bonded hydrogen in the polyorganosiloxane component containing silicon-bonded hydrogen (H) to the mole number of alkenyl groups in the polyorganosiloxane component containing alkenyl groups (Ak) can be adjusted in the range of 2 to 10. In another example, the range can 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 can be adjusted around 9 or less, 8 or less, or 7 or less.

[0076] This ratio may vary depending on the specific use of the curable composition.

[0077] For example, when the curable composition is a curing agent composition of a two-component curable composition, the ratio within the above range can be further adjusted within the 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 the range of 9 or less, 8.5 or less, 8 or less, 7.5 or less, or 7 or less.

[0078] In another example, when the curable composition is a mixed composition of a main composition of a two-component curable composition and a curing agent composition, or is a one-component composition, the ratio within the above range can be further adjusted within the range of 2.2 or more, 2.4 or more, 2.6 or more, or 2.8 or more and / or within the range of 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0079] When a thermally conductive filler is used as a filler in the curable composition, heat dissipation or thermal conductivity of the curable composition or a cured product thereof can be ensured.

[0080] Thermally conductive fillers are fillers that form a cured product that exhibits a thermal conductivity of about 1 W / mK or more in a curable composition using the filler. The thermal conductivity of the cured product may be about 1.2 W / mK or more, 1.4 W / mK or more, 1.6 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.

[0081] The filler component of the present application may have a filler having hydroxyl groups on the surface. In one example, the filler may be one or more selected from aluminum hydroxide (A1(OH)3), magnesium hydroxide (Mg(OH)2), calcium hydroxide (Ca(OH)2) and hydromagnesite (Mg5(CO3)4(OH)2·4H2O). These fillers have excellent thermal conductivity and low specific gravity, which is conducive to weight reduction. There is no particular restriction on the shape of the applicable filler, wherein for example, spherical fillers, such as needle-shaped or plate-shaped fillers or other amorphous fillers may also be used.

[0082] In one example, the filler having a hydroxyl group on the 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 by a method described in Examples to be described below. In another example, the average particle size of the filler can be greater than 0.005 μm, greater than 0.01 μm, greater than 0.05 μm, greater than 0.1 μm, greater than 0.5 μm, greater than 0.8 μm, greater than 1 μm, greater than 5 μm, greater than 10 μm, greater than 15 μm, greater than 20 μm, greater than 25 μm, greater than 30 μm, greater than 35 μm, greater than 40 μm, or greater than 45 μm, or can also be less than 95 μm, less than 90 μm, less than 85 μm, less than 80 μm, less than 75 μm, less than 70 μm, less than 65 μm, less than 60 μm, less than 55 μm, less than 50 μm, less than 45 μm, less than 40 μm, less than 35 μm, less than 30 μm, less than 25 μm, less than 20 μm, less than 15 μm, less than 10 μm, or less than 5 μm.

[0083] In order to ensure appropriate filling performance and to ensure desired physical properties, a mixture of two or more fillers having at least different average particle sizes can be used as fillers. For example, as fillers, a first filler having an average particle size of 20 μm or more and a second filler having an average particle size of 10 μm or less can also be used.

[0084] In another example, the average particle size of the first filler can be greater than 25 μm, greater than 30 μm, greater than 35 μm, greater than 40 μm, or greater than 45 μm, or can be less than 100 μm, less than 95 μm, less than 90 μm, less than 85 μm, less than 80 μm, less than 75 μm, less than 70 μm, less than 65 μm, less than 60 μm, or less than 55 μm.

[0085] Also, in another example, the average particle size of the second filler can be greater than 0.001 μm, greater than 0.005 μm, greater than 0.01 μm, greater than 0.05 μm, greater than 0.1 μm, greater than 0.5 μm, or greater than 0.8 μm, or can also be less than 10 μm, less than 8 μm, less than 6 μm, less than 4 μm, or less than 3 μm.

[0086] When the first filler and the second filler are used simultaneously, the ratio (D1 / D2) of the average particle size (D1) of the first filler to the average particle size (D2) of the second filler may be in the range of 2 to 200. In another example, 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 may be about 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.

[0087] When the first filler and the second filler are used at the same time, the ratio (W1 / W2) of the use weight of the first filler (W1) to the use weight of the second filler (W2) may be in the range of 0.5 to 10. In another example, the ratio (W1 / W2) may be 1 or more, 1.5 or more, or 2 or more, or may be 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or 3 or less.

[0088] The filler component may be included in an amount ranging from 200 to 900 parts by weight relative to 100 parts by weight of the alkenyl-containing polyorganosiloxane component of the curable composition. In addition, the filler component may be included in an amount ranging from 1,000 to 30,000 parts by weight relative to 100 parts by weight of the silicon-bonded hydrogen-containing polyorganosiloxane component of the curable composition.

[0089] When the above range is satisfied, it is possible to ensure long-term storage stability of the curable composition while ensuring excellent heat dissipation performance and improving the attachment force between the metal and the curable composition.

[0090] In one example, the content of the filler component can be 50 volume % to 75 volume % based on the total volume of the curable composition, and the volume ratio can be calculated in consideration of the mass ratio of each component contained in the curing agent composition and its density, and components not contained in the cured product of the final curing agent composition (for example, volatile components or solvents, etc.) are not considered in the above calculation.

[0091] The curable composition may contain other necessary components in addition to the above-mentioned components.

[0092] For example, the curable composition may further include a catalyst, for example, an addition reaction catalyst. The type of the catalyst is not particularly limited, but for example, a platinum-based catalyst may be used, wherein known or commercially available catalysts may be used as the platinum-based catalyst. The content of the catalyst is not particularly limited, wherein the amount of the catalyst that may be included depends on the composition of the curable polyorganosiloxane component.

[0093] In addition to the above components, the curable composition may further contain additional additives such as a pigment or dye, a dispersant, a thixotropic agent, a flame retardant, and the like, if necessary.

[0094] As described above, the curable composition may be a one-component composition, a main composition or a curing agent composition of a two-component composition, or a mixture of a main composition and a curing agent composition of a two-component composition.

[0095] In the case of a one-component composition or a mixture of a main composition and a curing agent composition of a two-component composition, the curable composition may contain the above components simultaneously.

[0096] Furthermore, when the curable composition is a main composition of a two-component composition, the main composition may contain an alkenyl group-containing polyorganosiloxane component as a curable polyorganosiloxane component, and may further contain a catalyst and a filler component.

[0097] In addition, when the resin composition is a curing agent composition of a two-component composition, the curing agent composition may contain an alkenyl-containing polyorganosiloxane component and a silicon-bonded hydrogen-containing polyorganosiloxane component, as a curable polyorganosiloxane component, and may further contain a filler component, and may not contain a catalyst. In this case, the fact that no catalyst is contained means that the catalyst is substantially not contained, which means that the catalyst is not intentionally added, and when the catalyst content is about 0.01% by weight or less, 0.001% by weight or less, 0.0001% by weight or less, or 0.00001% by weight or less based on the total weight of the composition, it can be said that the catalyst is substantially not contained.

[0098] In each of the above cases, specific types of the polyorganosiloxane component, filler component, catalyst, etc., and their formulation ratios are as described above.

[0099] In one example, when the resin composition is a two-component curable composition, the resin composition comprises a main composition and a curing agent composition, which are physically separated, wherein the main composition may comprise an alkenyl-containing polyorganosiloxane component and a filler component, and the curing agent composition may comprise an alkenyl-containing polyorganosiloxane component, a silicon-bonded hydrogen-containing polyorganosiloxane component, and a filler component.

[0100] In this case, the main composition may contain a catalyst and the curing agent composition may not contain a catalyst.

[0101] In one example, in the two-component curable composition, the ratio (Ak1 / Ak2) of the number of moles of alkenyl groups of the alkenyl-containing polyorganosiloxane component in the main composition (Ak1) to the number of moles of alkenyl groups of the alkenyl-containing polyorganosiloxane component in the curing agent composition (Ak2) 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 may be about 4 or less, 3.5 or less, 3 or less, 2.5 or less, 2 or less, or 1.5 or less.

[0102] 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) in 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 all 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 number of moles of silicon-bonded hydrogen atoms to the number of moles of alkenyl groups is adjusted to be within the above range, the advantage is 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 in 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 in the main composition and the curing agent composition.

[0103] In this case, specific types of the polyorganosiloxane component, filler component, catalyst, etc., and their formulation ratios are the same as described above.

[0104] In one example, the viscosity value of the two-component curable composition can be about 1,000,000 cP or less. The lower limit can be, for example, about 2,000 cP or more. For example, the viscosity value of the two-component curable composition can be about 950,000 cP or less, 900,000 cP or less, or about 850,000 cP or less, and can be about 3,000 cP or more, 4,000 cP or more, or about 5,000 cP or more. When the corresponding range is met, the long-term storage stability of the composition can be ensured, and appropriate processability can also be ensured.

[0105] The two-component curable composition of the present application may have the following physical properties suitable for use after curing.

[0106] In one example, the two-component curable composition may have a predetermined adhesive force at room temperature after curing. Specifically, the adhesive force to aluminum measured according to ASTM D1002 may be 3.8 kgf / cm 2 Above, 4.0kgf / cm 2 Above, 4.2kgf / cm 2 Above, 4.4kgf / cm 2 Above, 4.6kgf / cm 2 Above, 4.8kgf / cm 2 Above, 5.0kgf / cm 2 Above, 5.5kgf / cm 2 Above, 6.0kgf / cm 2 Above, or 6.5kgf / cm 2 There is no particular upper limit on the adhesion, but it can be, for example, 10.0 kgf / cm 2 Below, 9.0kgf / cm 2 Below, or 8.0kgf / cm 2 As described above, the two-component curable composition exhibits excellent adhesion to metals and can be effectively used in various applications requiring heat dissipation materials.

[0107] In an example, the two-component curable composition can have a predetermined hardness at room temperature after solidification. At this point, it is preferred that the cured layer of the composition show appropriate hardness. For example, if the hardness of the cured layer is too high, the cured layer has a brittle characteristic, thereby adversely affecting reliability. With this in mind, the hardness of the cured layer is adjusted, so that impact resistance and vibration resistance can be ensured, and the durability of the product can be ensured. In the cured layer, for example, Shore OO (Shore OO) type hardness can be more than 50, more than 55, more than 60, more than 65 or more than 70, and can be less than 90, less than 88, less than 86, less than 84 or less than 82. The hardness within the above range can be regulated by the content of filler and curing agent in the two-component curable composition.

[0108] In one example, the hardness (H0) of the two-component curable composition immediately after preparation (0 days) is different from the hardness (H0) when it is left at room temperature for more than 15 days (15 days). 15 ) ratio (H0 / H 15 ) can be 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, or 0.8 or more. 15 ) may be one of the Shore OO types, and the ratio (H0 / H0) may be adjusted by the content of filler and curing agent in the two-component curable composition. 15).

[0109] The two-component curable composition of the present application can be applied to various purposes requiring heat dissipation materials, and the scope of use is not particularly limited. For example, in battery-related technologies, the two-component curable composition can be applied to heat dissipation materials such as battery modules or battery packs, or heat dissipation materials for vehicles OBC (on-board charger). Therefore, the present application also relates to battery modules, battery packs or on-board chargers (OBC) containing the two-component curable composition or its cured product as heat dissipation materials. The application position or application method of the two-component curable composition or cured product in battery modules, battery packs or on-board chargers is not particularly limited, and known methods can be applied. In addition, the two-component curable composition of the present application is not limited to the above-mentioned uses, and it can be effectively applied to various uses requiring excellent heat dissipation performance, storage stability and adhesion.

[0110] In another example related to the present application, the present application may relate to an electronic device or device having a cured product of the two-component curable composition. The type of the electronic device or device is not particularly limited, and for example, it can be exemplified as an AVN (audio video navigation) module of a vehicle or an OBC (on-board charger) module of an electric vehicle, an LED module, or an IC chip and a computer or mobile device containing the same.

[0111] The cured product of the two-component curable composition can radiate heat within a device or apparatus, and can provide impact durability, insulation, and the like.

[0112] Beneficial Effects

[0113] In the present application, a curable composition having a simple manufacturing process, reduced manufacturing cost, and ensured long-term storage stability can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0114] Figure 1 : is a graph showing hardness change over storage period of cured products of curable compositions according to Examples 1 to 3 and Comparative Example 1. DETAILED DESCRIPTION

[0115] Hereinafter, the present application will be described in detail through examples, but the scope of the present application is not limited to the following examples.

[0116] 1. Hardness

[0117] The main composition and curing agent composition prepared in the embodiment or comparative example are placed in a two-component cartridge respectively; the main composition and curing agent composition are mixed in a volume ratio of 1:1 and cured into a film with a thickness of about 5 mm; then the hardness of the film surface is measured according to the ASTM D 2240 standard. When measuring the hardness, an ASKERDurometer instrument is used. The initial hardness is measured by applying a load of about 1.5 kg to the sample surface in a flat state, and the hardness is evaluated by confirming that the measured value is stable after 15 seconds. Shore OO hardness is measured.

[0118] 2. Thermal conductivity

[0119] The main composition and the curing agent composition prepared in the examples or comparative examples were placed in a two-component cartridge respectively; the main composition and the curing agent composition were mixed at a volume ratio of 1:1 and cured into a film having a thickness of about 5 mm; and then the thermal conductivity of the film in the thickness direction was measured. According to the standard of ISO22007-2, the thermal conductivity was measured using a device in a method of measuring temperature changes while heating a sensor having a nickel wire double helix structure as a hot plate measuring device.

[0120] 3. Viscosity

[0121] The viscosity of the main composition, curing agent composition or resin composition was measured using a viscoelasticity measuring device (Advanced Rheometic Expansion System; Brookfield, DV3T rheometer, CPA-52Z rotor). The temperature condition was set to room temperature (about 25 μ), the gap was set to 5 mm, and the viscosity was measured while changing the shear rate from 0.1 / s to 10.0 / s. The viscosity described below is the value when the shear rate is 1 / s.

[0122] 4. 1 H NMR analysis

[0123] Polyorganosiloxane component 1 H NMR analysis was performed in a known manner. The analysis was performed at room temperature using an NMR spectrometer comprising a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. The analyte polyorganosiloxane component was diluted in a solvent (CDCl3) to a concentration of about 10 mg / ml for NMR measurement and used, and the chemical shift was expressed in ppm.

[0124] 5. 29 Si NMR analysis

[0125] Polyorganosiloxane component 29 Si NMR analysis was performed in a known manner. 29In Si NMR analysis, TMS (tetramethylsilane diluted in CDCl3) was used as a reference compound to express chemical shifts.

[0126] 6. GPC (Gel Permeation Chromatography)

[0127] The number-average molecular weight (Mn) and molecular weight distribution of the polyorganosiloxane component were determined using GPC (Gel Permeation Chromatography). The analyte polyorganosiloxane was placed in a 5 mL vial and diluted to a concentration of approximately 5 mg / mL in THF (tetrahydrofuran). Then, the calibration standard samples and the samples to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) and measured. As the analysis procedure, Agilent Technologies' ChemStation was used. By comparing the elution times of the samples with the calibration curve, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were obtained respectively, and the molecular weight distribution (PDI) was calculated by the ratio (Mw / Mn). The measurement conditions for GPC are as follows.

[0128] <GPC Measurement Conditions>

[0129] Instrument: Agilent Technologies 1200 series

[0130] Columns: 2 Polymer Laboratories' PLgel mixed B were used

[0131] Solvent: THF (tetrahydrofuran)

[0132] Column temperature: 40 μ

[0133] Sample concentration: 5 mg / mL, 10 μL injected

[0134] Standard samples: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

[0135] Example 1

[0136] Preparation of the master composition

[0137] In the main part of 10 g, 7.92 g of a polyorganosiloxane component (VP1000, Damipolychem) with a viscosity of 1000 cP and a polyorganosiloxane containing the following formula A, 1.98 g of a polyorganosiloxane component (DSVP100, Double S Solution) with a viscosity of 100 cP and a polyorganosiloxane containing the following formula B and 0.1 g of a platinum catalyst (1,3-divinyl-1,1,3,3-tetramethyl-disiloxane-platinum (0)-complex), aluminum hydroxide having a D50 particle size of about 50 μm and aluminum hydroxide having a D50 particle size of about 1 μm were mixed in a weight ratio of 7:3. The content of the mixed aluminum hydroxide filler was 475 parts by weight relative to 100 parts by weight of the polyorganosiloxane component containing the polyorganosiloxanes of formula A and formula B.

[0138] The polyorganosiloxane component comprising the polyorganosiloxane of formula A measured in the above manner 1 In the H-NMR analysis, the area ratio of the Si-CH3 to Si-vinyl peaks (Si-CH3 / Si-vinyl) was about 252, and the content of vinyl determined on this basis was about 0.107 mmol / g. 1 In the H-NMR analysis, the area ratio of the Si-CH3 to Si-vinyl peaks (Si-CH3 / Si-vinyl) was about 93, and the vinyl content determined on this basis was about 0.29 mmol / g.

[0139] The number average molecular weight (Mn) of the polyorganosiloxane component containing the polyorganosiloxane of formula A determined by GPC is about 14,800 g / mol; the weight average molecular weight (Mw) is about 35,500 g / mol; and the molecular weight distribution (PDI=Mw / Mn) is about 2.40. The number average molecular weight (Mn) of the polyorganosiloxane component containing the polyorganosiloxane of formula B determined by GPC is about 7,020 g / mol; the weight average molecular weight (Mw) is about 13,700 g / mol; and the molecular weight distribution (PDI=Mw / Mn) is about 1.95.

[0140] The components were introduced into a pulp mixer, mixed and dispersed at 600 rpm and 500 rpm for about 3 minutes, and then the main composition was prepared by confirming the heat generated and defoaming the mixture at 600 rpm and 200 rpm for 4 minutes under vacuum.

[0141] [Formula A]

[0142]

[0143] In formula A, m is a number of about 250.

[0144] [Formula B]

[0145]

[0146] In formula B, n is a number of about 91.

[0147] Preparation of curing agent composition

[0148] In 10 g of the curing agent portion, 6.12 g of a polyorganosiloxane component comprising the polyorganosiloxane of the above-mentioned formula A, 1.53 g of a polyorganosiloxane component comprising the above-mentioned formula B, 0.35 g of a polyorganosiloxane component comprising the following formula C (XL11, AB Specialty Silicones) and 2 g of a polyorganosiloxane component comprising the following formula D (CE4, AB Specialty Silicones) were included, and aluminum hydroxide having a D50 particle size of about 50 μm and aluminum hydroxide having a D50 particle size of about 1 μm were mixed in a weight ratio of 7:3. The content of the mixed aluminum hydroxide filler was 614 parts by weight relative to 100 parts by weight of the polyorganosiloxane component comprising the polyorganosiloxanes of the formulas A and B, and the content of the mixed aluminum hydroxide filler was 2000 parts by weight relative to 100 parts by weight of the polyorganosiloxane component comprising the polyorganosiloxanes of the formulas C and D.

[0149] As a polyorganosiloxane component comprising a polyorganosiloxane of formula C 29 Si NMR analysis shows that the M units ((CH3)3SiO 1 / 2 The molar ratio of the D unit ((CH3)2SiO 2 / 2 The molar ratio of the D unit (H(CH3)SiO 2 / 2 The molar ratio of units) is about 26.9 mol%. In addition, by 1 The ratio of the Si-CH3 peak to the Si-H peak (Si-CH3 / Si-H) determined by H NMR analysis was about 19.2, and the content of silicon-bonded hydrogen determined therefrom was about 4.14 mmol / g.

[0150] In addition, by subjecting the polyorganosiloxane component comprising the polyorganosiloxane of formula D to 1 The ratio of the Si-CH3 peak to the Si-H peak (Si-CH3 / Si-H) determined by H NMR analysis was about 34.2, and the content of silicon-bonded hydrogen determined therefrom was about 2.9 mmol / g.

[0151] The components were introduced into a slurry mixer, mixed and dispersed at 600 rpm and 500 rpm for about 3 minutes, and then the curing agent composition was prepared by confirming the heat generated and defoaming the mixture at 600 rpm and 200 rpm for 4 minutes under a vacuum state.

[0152] [Formula C]

[0153]

[0154] In formula C, p is a number approximately 32, and q is a number approximately 13.

[0155] [Formula D]

[0156]

[0157] In formula D, n is a number of about 9.

[0158] In each of the main composition and the curing agent composition, the content of aluminum hydroxide was 65 volume %, and the compositions were mixed so that the molar ratio (B / A) of the silicon-bonded hydrogen (B) of the curing agent composition to the alkenyl group (A) of the main composition and the curing agent composition was 2.88, thereby preparing a curable composition.

[0159] Example 2

[0160] Preparation of the master composition

[0161] The main composition prepared in Example 1 above was used.

[0162] Preparation of curing agent composition

[0163] A curable composition was prepared in the same manner as in Example 1, except that the curing agent portion was prepared to include 6.52 g of a polyorganosiloxane component comprising a polyorganosiloxane of Formula A, 1.63 g of a polyorganosiloxane component comprising a polyorganosiloxane of Formula B, 0.35 g of a polyorganosiloxane component comprising a polyorganosiloxane of Formula C (XL11, AB Specialty Silicones), and 1.5 g of a polyorganosiloxane component comprising a polyorganosiloxane of Formula D (CE4, AB Specialty Silicones), which was used in the preparation of the curing agent composition in Example 1.

[0164] In each of the main composition and the curing agent composition, the content of aluminum hydroxide was 65 volume %, and the compositions were mixed so that the molar ratio (B / A) of the silicon-bonded hydrogen (B) of the curing agent composition to the alkenyl groups (A) of the main composition and the curing agent composition was 1.72, thereby preparing a curable composition.

[0165] Example 3

[0166] Preparation of the master composition

[0167] In the main part of 10 g, 9.98 g of a polyorganosiloxane component (VP1000, Damipolychem) containing a polyorganosiloxane of formula A and 0.02 g of a platinum catalyst (1,3-divinyl-1,1,3,3-tetramethyl-disiloxane-platinum (0)-complex) used in the preparation of the main composition in Example 1 above 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 content of the mixed aluminum hydroxide filler was 301 parts by weight relative to 100 parts by weight of the polyorganosiloxane component containing polyorganosiloxanes of formulas A and B.

[0168] Preparation of curing agent composition

[0169] In 10 g of the curing agent portion, 5 g of a polyorganosiloxane component comprising a polyorganosiloxane of formula A, 1.67 g of a polyorganosiloxane component comprising a polyorganosiloxane of formula C (XL11, AB Specialty Silicones) and 3.33 g of a polyorganosiloxane component comprising a polyorganosiloxane of formula D (CF4, AB Specialty Silicones, which was used in preparing the main composition in Example 1 above, aluminum hydroxide having a D50 particle size of about 50 μm and aluminum hydroxide having a D50 particle size of about 1 μm were mixed at a weight ratio of 7:3. The content of the mixed aluminum hydroxide filler was 600 parts by weight relative to 100 parts by weight of the polyorganosiloxane component comprising the polyorganosiloxanes of formulas C and D.

[0170] The components were introduced into a slurry mixer, mixed and dispersed at a speed of 600 rpm and 500 rpm for about 3 minutes, and then a curing agent composition was prepared by confirming the heat generated and defoaming the mixture at a speed of 600 rpm and 200 rpm for 4 minutes under a vacuum state.

[0171] In each of the main composition and the curing agent composition, the content of aluminum hydroxide was 54 volume %, and the compositions were mixed so that the molar ratio (B / A) of the silicon-bonded hydrogen (B) of the curing agent composition to the alkenyl groups (A) of the main composition and the curing agent composition was 3.81, thereby preparing a curable composition.

[0172] Comparative Example 1

[0173] Preparation of the master composition

[0174] In the main part of 10 g, 8.18 g of a polyorganosiloxane component (VP1000, Damipolychem) with a viscosity of 1000 cP and a polyorganosiloxane containing the following formula A, 1.67 g of a polyorganosiloxane component (DSVP100, Double S Solution) with a viscosity of 100 cP and a polyorganosiloxane containing the following formula B and 0.15 g of a platinum catalyst (1,3-divinyl-1,1,3,3-tetramethyl-disiloxane-platinum (0)-complex), aluminum hydroxide having a D50 particle size of about 50 μm and aluminum hydroxide having a D50 particle size of about 1 μm were mixed in a weight ratio of 7:3. The content of the mixed aluminum hydroxide filler was 477 parts by weight relative to 100 parts by weight of the polyorganosiloxane component containing the polyorganosiloxanes of formula A and formula B.

[0175] The components were introduced into a pulp mixer, mixed and dispersed at 600 rpm and 500 rpm for about 3 minutes, and then the main composition was prepared by confirming the heat generated and defoaming the mixture at 600 rpm and 200 rpm for 4 minutes under vacuum.

[0176] [Formula A]

[0177]

[0178] In formula A, m is a number of about 250.

[0179] [Formula B]

[0180]

[0181] In formula B, n is a number of about 91.

[0182] Preparation of curing agent composition

[0183] In 10 g of the curing agent portion, 7.96 g of a polyorganosiloxane component comprising the polyorganosiloxane of the above-mentioned formula A and 1.67 g of a polyorganosiloxane component comprising the polyorganosiloxane of the above-mentioned formula B, 0.37 g of a polyorganosiloxane component comprising the polyorganosiloxane of the following formula C (FD5020, DamiPolychem), aluminum hydroxide having a D50 particle size of about 50 μm and aluminum hydroxide having a D50 particle size of about 1 μm were mixed in a weight ratio of 7:3. The content of the mixed aluminum hydroxide filler was 488 parts by weight relative to 100 parts by weight of the polyorganosiloxane component comprising the polyorganosiloxane of formula A and formula B, and the content of the mixed aluminum hydroxide filler was 12,703 parts by weight relative to 100 parts by weight of the polyorganosiloxane component comprising the polyorganosiloxane of formula C.

[0184] The components were introduced into a slurry mixer, mixed and dispersed at a speed of 600 rpm and 500 rpm for about 3 minutes, and then a curing agent composition was prepared by confirming the heat generated and defoaming the mixture at a speed of 600 rpm and 200 rpm for 4 minutes under a vacuum state.

[0185] [Formula C]

[0186]

[0187] In formula C, p is a number of about 39, and q is a number of about 8.

[0188] In each of the main composition and the curing agent composition, the content of aluminum hydroxide is 65 volume %, and the compositions are mixed so that the molar ratio (B / A) of the silicon-bonded hydrogen (B) of the curing agent composition to the alkenyl group (A) of the main composition and the curing agent composition is 0.4, thereby preparing a curable composition.

[0189] For storage stability evaluation, the thermal conductivity and hardness of the curable composition of Comparative Example 1 were evaluated immediately after preparation (0d), 3 days after (3d), 9 days after (9d), and 15 days after (15d), and are summarized in the following Table 1. In addition, the thermal conductivity and hardness immediately after the preparation of the curable compositions of Examples 1 to 3 and after a period of time are summarized in Table 1.

[0190] [Table 1]

[0191]

[0192]

[0193] refer to Figure 1 From Table 1, it can be confirmed that the hardness of the curable composition of Comparative Example 1 decreased by more than 20 within 10 days after preparation, but the curable compositions of Examples 1 to 3 decreased in hardness over time to a small extent and exhibited appropriate thermal conductivity, thereby ensuring storage stability.

Claims

1. A two-component curable composition comprising a main composition and a curing agent composition, wherein The main composition comprises an alkenyl-containing polyorganosiloxane component and a filler component, wherein the filler component comprises a filler having a hydroxyl group on the surface, and The curing agent composition comprises an alkenyl-containing polyorganosiloxane component, a silicon-bonded hydrogen-containing polyorganosiloxane component and a filler component, wherein the filler component comprises a filler having a hydroxyl group on the surface, wherein: the volume ratio of the filler component is 50 volume % to 75 volume %, the alkenyl content of the alkenyl-containing polyorganosiloxane component is in the range of 0.05 mmol / g to 5 mmol / g, the ratio (H / Ak) of the number of moles of silicon-bonded hydrogen contained in the silicon-bonded hydrogen-containing polyorganosiloxane component in the curing agent composition (H) to the number of moles of alkenyl groups contained in the main composition and the alkenyl-containing polyorganosiloxane component in the curing agent composition (Ak) is in the range of 1.72 to 3.81, The silicon-bonded hydrogen-containing polyorganosiloxane component comprises a first polyorganosiloxane component having a compound of the following formula 2; and a second polyorganosiloxane component having a compound of the following formula 3: [Formula 2] Wherein, R3 is an alkyl group, and m is a number in the range of 7 to 25: [Formula 3] wherein R4 is an alkyl group, p is a number in the range of 20 to 60, q is a number in the range of 3 to 20, Wherein, the ratio (H1 / H2) of the molar number of silicon-bonded hydrogen in the first polyorganosiloxane component (H1) to the molar number of silicon-bonded hydrogen in the second polyorganosiloxane component (H2) is in the range of 0.5 to 10.

2. The two-component curable composition according to claim 1, wherein The ratio (Ak1 / Ak2) of the molar number of alkenyl groups of the alkenyl-containing polyorganosiloxane component in the main composition (Ak1) to the molar number of alkenyl groups of the alkenyl-containing polyorganosiloxane component in the curing agent composition (Ak2) is in the range of 0.5 to 5.

3. The two-component curable composition according to claim 1, wherein The main composition also includes a catalyst.

4. The two-component curable composition according to claim 1, wherein The alkenyl-containing polyorganosiloxane component of the curing agent composition has a polyorganosiloxane represented by the following Formula 1: [Formula 1] wherein R5 is an alkenyl group, R6 is an alkyl group, and n is a number in the range of 30 to 300.

5. The two-component curable composition according to claim 1, wherein The content of silicon-bonded hydrogen in the first polyorganosiloxane component of the curing agent composition is in the range of 0.5 mmol / g to 10 mmol / g, and the content of silicon-bonded hydrogen in the second polyorganosiloxane component is in the range of 0.5 mmol / g to 6 mmol / g.

6. The two-component curable composition according to claim 1, wherein The filler of the curing agent composition is an inorganic hydroxide.

7. The two-component curable composition according to claim 6, wherein: The filler component of the curing agent composition includes 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.

8. The two-component curable composition according to claim 7, wherein A ratio (D1 / D2) of an average particle size (D1) of the first inorganic hydroxide to an average particle size (D2) of the second inorganic hydroxide is in the range of 2 to 200.

9. The two-component curable composition according to claim 7, wherein: A ratio (W1 / W2) of the weight of the first inorganic hydroxide (W1) to the weight of the second inorganic hydroxide (W2) is in the range of 0.5 to 10.

10. The two-component curable composition according to claim 1, wherein: The ratio of the filler component in the curing agent composition is in the range of 300 parts by weight to 900 parts by weight relative to 100 parts by weight of the alkenyl group-containing polyorganosiloxane component in the curing agent composition.

11. The two-component curable composition according to claim 1, wherein: The ratio of the filler component in the curing agent composition is in the range of 1,000 parts by weight to 30,000 parts by weight relative to 100 parts by weight of the polyorganosiloxane component containing silicon-bonded hydrogen in the curing agent composition.

12. The two-component curable composition according to claim 1, wherein: The curing agent composition does not contain a catalyst.

13. A curable composition comprising: an alkenyl-containing polyorganosiloxane component; a polyorganosiloxane component containing silicon-bonded hydrogen; and A filler component, the filler component having a filler having hydroxyl groups on the surface, wherein The volume ratio of the filler component is 50 volume % to 75 volume %, The alkenyl content of the alkenyl-containing polyorganosiloxane component is in the range of 0.05 mmol / g to 5 mmol / g, and the ratio (H / Ak) of the number of moles of silicon-bonded hydrogen (H) contained in the polyorganosiloxane component containing silicon-bonded hydrogen to the number of moles of alkenyl groups (Ak) contained in the polyorganosiloxane component containing alkenyl groups is in the range of 1.72 to 3.81, in, The silicon-bonded hydrogen-containing polyorganosiloxane component comprises a first polyorganosiloxane component having a compound of Formula 2 below; and a second polyorganosiloxane component having a compound of Formula 3 below: [Formula 2] Wherein, R3 is an alkyl group, and m is a number in the range of 7 to 25: [Formula 3] wherein R4 is an alkyl group, p is a number in the range of 20 to 60, q is a number in the range of 3 to 20, Wherein, the ratio (H1 / H2) of the molar number of silicon-bonded hydrogen in the first polyorganosiloxane component (H1) to the molar number of silicon-bonded hydrogen in the second polyorganosiloxane component (H2) is in the range of 0.5 to 10.

14. The curable composition according to claim 13, wherein The alkenyl-containing polyorganosiloxane component has a polyorganosiloxane represented by the following Formula 1: [Formula 1] wherein R5 is an alkenyl group, R6 is an alkyl group, and n is a number in the range of 30 to 300.

15. The curable composition according to claim 13, wherein The content of silicon-bonded hydrogen in the first polyorganosiloxane component is in the range of 0.5 mmol / g to 10 mmol / g, and the content of silicon-bonded hydrogen in the second polyorganosiloxane component is in the range of 0.5 mmol / g to 6 mmol / g.

16. The curable composition according to claim 13, wherein The filler is an inorganic hydroxide.

17. The curable composition according to claim 16, wherein The filler component includes 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.

18. The curable composition according to claim 17, wherein A ratio (D1 / D2) of an average particle size (D1) of the first inorganic hydroxide to an average particle size (D2) of the second inorganic hydroxide is in the range of 2 to 200.

19. The curable composition according to claim 17, wherein A ratio (W1 / W2) of the weight of the first inorganic hydroxide (W1) to the weight of the second inorganic hydroxide (W2) is in the range of 0.5 to 10.

20. The curable composition according to claim 13, wherein The ratio of the filler component is in the range of 200 to 900 parts by weight relative to 100 parts by weight of the alkenyl group-containing polyorganosiloxane component.

21. The curable composition according to claim 13, wherein The ratio of the filler component is in the range of 1,000 parts by weight to 30,000 parts by weight relative to 100 parts by weight of the silicon-bonded hydrogen-containing polyorganosiloxane component.

22. The curable composition according to claim 13, wherein The curable composition is free of catalyst.

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