Thermally-conductive silicone-based composition and cured product thereof

Abstract

A thermally-conductive silicone-based composition according to one embodiment of the present invention comprises: 1) a first polysiloxane including at least one alkenyl group; 2) a second polysiloxane including at least one hydrogen group; 3) a hydrosilylation catalyst; and 4) a filler, wherein the filler includes a first alumina having an average particle diameter of 0.1 μm or greater and less than 1 μm and a specific surface area of 6 m2 / g to 8 m2 / g, and the amount of the first alumina is 5-25 wt% on the basis of the total weight of the filler.

Description

Thermally conductive silicon-based composition and cured product thereof

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2024-0153220 filed with the Korean Intellectual Property Office on November 1, 2024, the entire contents of which are incorporated herein.

[0002] The present invention relates to a thermally conductive silicon-based composition and a cured product thereof.

[0003] Thermally conductive adhesives are used in electronic components, such as power transistors, ICs (Integrated Circuits), and CPUs (Central Processing Units), to prevent heat accumulation in heating elements.

[0004] Silicone rubber is widely used in the above-mentioned thermally conductive adhesives. However, since silicone alone cannot increase thermal conductivity, thermally conductive fillers are used in combination to improve the thermal conductivity of silicone rubber. As such thermally conductive fillers, materials with higher thermal conductivity than silicone, such as alumina, boron nitride, aluminum nitride, and magnesium oxide, are known.

[0005] As recent electronic components increase in power output, they generate more heat, necessitating heat dissipation materials with higher thermal conductivity. To obtain silicon compositions with high thermal conductivity to meet this demand, it is necessary to increase the filling of thermally conductive fillers. However, there are limitations to such filling capacity due to factors such as reduced fluidity.

[0006] Thermally conductive materials consist of thermally conductive fillers for high thermal conductivity and silicone compositions for mechanical properties. Basically, to achieve high thermal conductivity, the content of thermally conductive fillers is increased or angular-shaped fillers are used; however, this leads to higher rheological properties, particularly viscosity, which adversely affects the dispersibility of the product. Since this significantly impacts workability during product dispensing and can cause reliability issues, there is a need to develop well-dispersed materials with a viscosity level that allows for workability.

[0007] The present invention aims to solve these problems by providing a thermally conductive silicon-based composition with improved dispersibility while maintaining high thermal conductivity and conventional mechanical properties.

[0008] One embodiment of the present invention is,

[0009] 1) A first polysiloxane comprising at least one alkenyl group;

[0010] 2) A second polysiloxane comprising at least one hydrogen group;

[0011] 3) Hydrosilylation catalyst; and

[0012] 4) Includes filler,

[0013] The above filler has an average particle size of 0.1㎛ or more and less than 1㎛, and a specific surface area of ​​6 m² 2 / g to 8 m 2 It includes a first alumina of / g,

[0014] A thermally conductive silicon-based composition is provided, wherein the content of the first alumina is 5% to 25% by weight based on the total weight of the filler.

[0015] In addition, another embodiment of the present invention provides a cured product obtained by curing the thermally conductive silicon-based composition.

[0016] In addition, another embodiment of the present invention provides an electronic device comprising the cured material.

[0017] According to one embodiment of the present invention, a thermally conductive silicon-based composition with improved dispersibility can be provided while maintaining high thermal conductivity and conventional mechanical properties.

[0018] A thermally conductive silicon-based composition according to one embodiment of the present invention has excellent flowability, so it can be applied as a heat dissipation material in electronic components such as various electronic devices that require excellent workability. In particular, a thermally conductive silicon-based composition according to one embodiment of the present invention can be more suitablely applied to TIM1 (Thermal Interface Material 1) in which a lid attach is performed by applying a snap cure process.

[0019] FIG. 1 is a schematic diagram showing a semiconductor package to which a thermally conductive silicon-based composition according to one embodiment of the present invention is applied.

[0020] The present application will be described in detail below.

[0021] Thermally conductive materials consist of thermally conductive fillers for high thermal conductivity and silicone compositions for mechanical properties. Basically, to achieve high thermal conductivity, the content of thermally conductive fillers is increased or angular-shaped fillers are used; however, this leads to higher rheological properties, particularly viscosity, which adversely affects the dispersibility of the product. Since this significantly impacts workability during product dispensing and can cause reliability issues, there is a need to develop well-dispersed materials with a viscosity level that allows for workability.

[0022] The present invention aims to solve these problems by providing a thermally conductive silicon-based composition with improved dispersibility while maintaining high thermal conductivity and conventional mechanical properties.

[0023] In the present invention, it was discovered that when a thermally conductive filler is included in a combination of thermally conductive silicon-based compositions, the dispersibility of the silicon-based composition is improved when a filler having a specific specific surface area is included.

[0024] A thermally conductive silicon-based composition according to one embodiment of the present invention comprises: 1) a first polysiloxane comprising at least one alkenyl group; 2) a second polysiloxane comprising at least one hydrogen group; 3) a hydrosilylation catalyst; and 4) a filler, wherein the filler has an average particle size of 0.1 μm or more and less than 1 μm and a specific surface area of ​​6 m² 2 / g to 8 m 2 It is characterized by including a first alumina of 1 / g, wherein, based on the total weight of the filler, the content of the first alumina is 5% to 25% by weight.

[0025] In one embodiment of the present invention, the first polysiloxane may be represented by the following chemical formula 1.

[0026] [Chemical Formula 1]

[0027] (R 1a R 2a R 3a SiO 1 / 2 ) aa (R 4a R 5a SiO 2 / 2 ) ba (R 6a SiO 3 / 2 ) ca (SiO 4 / 2 ) da

[0028] In the above chemical formula 1,

[0029] R 1a to R 6a At least one of them is an alkenyl group, and

[0030] The remainders are identical or different from one another, each independently an alkyl group, an alkoxy group, an aryl group, or a silanol group, which are substituted or unsubstituted with a halogen, and

[0031] aa + ba + ca + da = 1, 0 ≤ aa < 1, 0 ≤ ba < 1, 0 ≤ ca < 1, 0 ≤ da < 1 is satisfied.

[0032] The above-mentioned first polysiloxane may include one or more types or two or more types.

[0033] In one embodiment of the present invention, the second polysiloxane may be represented by the following chemical formula 2.

[0034] [Chemical Formula 2]

[0035] (R 1b R 2b R 3b SiO 1 / 2 ) ab (R 4b R 5b SiO 2 / 2 ) bb (R 6b SiO 3 / 2 ) cb (SiO 4 / 2 ) db

[0036] In the above chemical formula 2,

[0037] R 1b to R 6b At least one of them is a hydrogen group, and

[0038] The remainders are identical or different from one another, each independently an alkyl group, an alkoxy group, an aryl group, or a silanol group, which are substituted or unsubstituted with a halogen, and

[0039] ab + bb + cb + db = 1, 0 ≤ ab < 1, 0 ≤ bb < 1, 0 ≤ cb < 1, 0 ≤ db < 1 is satisfied.

[0040] The above second polysiloxane may include one or more types or two or more types.

[0041] Silicone-based resins having a siloxane structure (Si-O-Si) are classified into monofunctional silicone units (M units), difunctional silicone units (D units), trifunctional silicone units (T units), and tetrafunctional silicone units (Q units) according to their constituent units, and these units are used individually or in a copolymerized state. Structures composed solely of monofunctional and difunctional silicone units exist in the form of linear siloxanes; as the content of difunctional silicone units increases, the linear length lengthens, and the viscosity increases accordingly. Even when viscosity increases to the maximum, the material does not solidify, and at a level where synthesis is possible, it takes on a shape similar to raw rubber.

[0042] According to one embodiment of the present invention, the content of the first polysiloxane and the second polysiloxane can be controlled to adjust the degree of networking when forming a cured product of the final silicone-based composition by controlling the content of the monofunctional M unit, the difunctional D unit, the trifunctional T unit, and the tetrafunctional Q unit, and the hardness of the cured product can be controlled according to this content. Accordingly, in one embodiment of the present invention, the ratio of the moles per unit weight of the alkenyl group contained in the first polysiloxane to the moles per unit weight of the hydrogen group contained in the second polysiloxane can range from 0.5 to 3.

[0043] In one embodiment of the present invention, the alkyl group may be straight, branched, or cyclic, and the number of carbon atoms is not particularly limited but is preferably 1 to 30. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, cyclopentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, cyclohexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, There are, but are not limited to, 2-propylpentyl groups, n-nonyl groups, 2,2-dimethylheptyl groups, 1-ethyl-propyl groups, 1,1-dimethyl-propyl groups, isohexyl groups, 2-methylpentyl groups, 4-methylhexyl groups, 5-methylhexyl groups, etc.

[0044] The above aryl group may be monocyclic or polycyclic, and while the number of carbon atoms is not particularly limited, it is preferable to have 6 to 30 carbon atoms. Specific examples may include, but are not limited to, phenyl groups, biphenyl groups, terphenyl groups, naphthyl groups, triphenylenyl groups, anthracenyl groups, phenanthryl groups, pyrenyl groups, perylenyl groups, chrysenyl groups, fluorenyl groups, etc.

[0045] The above halogen group can be fluorine, chlorine, bromine, or iodine.

[0046] The above alkoxy group may be a straight chain, a branched chain, or a cyclic chain. The number of carbon atoms in the above alkoxy group is not particularly limited, but it is preferable to have 1 to 20 carbon atoms. Specifically, it may be a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a sec-butoxy group, an n-pentyloxy group, a neopentyloxy group, an isopentyloxy group, an n-hexyloxy group, a 3,3-dimethylbutyloxy group, a 2-ethylbutyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, a benzyloxy group, a p-methylbenzyloxy group, etc., but is not limited thereto.

[0047] The above alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1-butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but are not limited to these.

[0048] In one embodiment of the present application, the hydrosilylation catalyst is a catalyst for a hydrosilylation reaction to promote the curing of a composition. Examples of the hydrosilylation catalyst include platinum group element catalysts and platinum group element compound catalysts, and specifically, may include one or more of platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. In particular, it is preferable that the catalyst be a platinum-based catalyst, as it can significantly promote the curing of the composition. Examples of the above platinum-based catalysts include platinum fine powder, platinum black, chloroplatinic acid, alcohol modified product of chloroplatinic acid, complex of chloroplatinic acid and diolefin, platinum-olefin complex, platinum-carbonyl complex such as platinum-bis(acetoacetate) and platinum-bis(acetylacetonate), chloroplatinic acid-alkenylsiloxane complex such as chloroplatinic acid-divinyltetramethyldisiloxane complex and chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, platinum-alkenylsiloxane complex such as platinum-divinyltetramethyldisiloxane complex and platinum-tetravinyltetramethylcyclotetrasiloxane complex, complex of chloroplatinic acid with acetylene alcohols, and mixtures of two or more of these.

[0049] In one embodiment of the present invention, the filler has an average particle size of 0.1 μm or more and less than 1 μm, and a specific surface area of ​​6 m² 2 / g to 8 m 2 It contains a first alumina of / g.

[0050] The first alumina has an average particle size of 0.1㎛ or more and less than 1㎛, and a specific surface area of ​​6 m² 2 / g to 8 m 2 By satisfying the characteristic of / g, the fluidity of the silicon-based composition containing the first alumina can be more effectively improved. The specific surface area of ​​the first alumina is 6 m² 2 If it is less than / g, it is undesirable because wettability with silicon is not sufficiently expressed, which may lead to reduced fluidity. In addition, the specific surface area of ​​the first alumina is 8 m² 2If it exceeds / g, fluidity may decrease due to an increase in viscosity and thixotropic factors, so it is not desirable.

[0051] The above first alumina may include one or more types or two or more types.

[0052] In one embodiment of the present invention, the filler may further include, in addition to the first alumina, one or more of a second filler having an average particle size of 1 μm or more and less than 10 μm, and a third filler having an average particle size of 10 μm or more and less than 100 μm. Additionally, in addition to the first alumina, the filler may have an average particle size of 0.1 μm or more and less than 1 μm, and a specific surface area of ​​6 m² 2 It may further include a fourth filler less than / g. That is, the filler may include a first alumina and a second filler, may include a first alumina and a third filler, may include a first alumina, a second filler and a third filler, and may include a first alumina, a second filler, a third filler and a fourth filler.

[0053] The second, third, and fourth fillers mentioned above may be alumina, and inorganic fillers known in the art, such as magnesium oxide, zinc oxide, boron nitride, aluminum nitride, silicon carbide, metal powder, diamond, aluminum hydroxide, carbon, etc., may also be used. It is more preferable that the second, third, and fourth fillers be alumina.

[0054] If only particles of the same size are used as the filler, a relatively large amount of space remains between the particles, making efficient filling difficult. However, if small particles fill the empty spaces between large particles, the overall filling density increases and space utilization can be maximized. As a result, the fillers are stacked more densely, but the small particles act like bearings between the large particles, providing space for them to roll or slide against each other, and this structure can contribute to improving fluidity. Therefore, in addition to the first alumina, it is preferable for the filler to further include a second filler with an average particle size of 1㎛ or more and less than 10㎛, and a third filler with an average particle size of 10㎛ or more and less than 100㎛.

[0055] In particular, it is more preferable that the above filler further includes, in addition to the first alumina, a second alumina with an average particle size of 1 µm or more and less than 10 µm, and a third alumina with an average particle size of 10 µm or more and less than 100 µm.

[0056] The shape of the particles, such as the first alumina and the first to fourth fillers, that can be applied as the above filler is not particularly limited. For example, the particles, such as the first alumina and the first to fourth fillers, that can be applied as the above filler may be spherical, irregular, or roundish in shape, but are not limited thereto.

[0057] In one embodiment of the present invention, the average particle size of the particles of the first alumina, the first to fourth fillers, etc., which can be applied as the filler, refers to D50, which is an intermediate particle size.

[0058] In one embodiment of the present invention, based on the total weight of the filler, the content of the first alumina may be 5% to 25% by weight and 10% to 20% by weight. Based on the total weight of the filler, if the content of the first alumina is less than 5% by weight, the effect of improving fluidity may be negligible, and if it exceeds 25% by weight, the viscosity and thixotropy may increase, and the effect of improving fluidity may decrease, so it is not desirable.

[0059] In one embodiment of the present invention, based on the total weight of the thermally conductive silicon-based composition, the content of the first polysiloxane may be 0.1 wt% to 10 wt%, the content of the second polysiloxane may be 0.1 wt% to 10 wt%, the content of the hydrosilylation catalyst may be 0.0001 wt% to 0.1 wt%, and the content of the filler may be 80 wt% to 98 wt%. In addition, in another embodiment of the present invention, based on the total weight of the thermally conductive silicon-based composition, the content of the first polysiloxane may be 1% to 6% by weight, the content of the second polysiloxane may be 1% to 6% by weight, the content of the hydrosilylation catalyst may be 0.001% to 0.1% by weight, and the content of the filler may be 88% to 97% by weight.

[0060] In one embodiment of the present invention, the thermally conductive silicone-based composition may further include one or more of a dispersant, a retardant, and an adhesion promoter.

[0061] The above-mentioned dispersant is a low-molecular-weight substance having a siloxane structure and a viscosity of 500 mPa·s or less, and may include hydrophilic silanol groups, alkoxy groups, hydrogen groups, etc., and may be synthesized or a silicone-based silane coupling agent may be used. However, if a monomer with a molecular weight too low is used, it may vaporize due to the vacuum and temperature during the high-temperature dispersion process that may be performed to improve dispersibility, so countermeasures must be taken for this.

[0062] More specifically, the above dispersant can be represented by the following chemical formula 3.

[0063] [Chemical Formula 3]

[0064]

[0065] In the above chemical formula 3,

[0066] R 1 It is a group containing an alkoxysiloxy group having 1 to 4 carbon atoms, and

[0067] R 2 is a siloxane represented by the following chemical formula 3-1 or a monovalent hydrocarbon group having 6 to 18 carbon atoms, and

[0068] X is each independently a divalent hydrocarbon group having 2 to 10 carbon atoms, and

[0069] R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and

[0070] a and b are each independently integers greater than or equal to 1, c is an integer greater than or equal to 0, and (a+b+c) is an integer greater than or equal to 4, and

[0071] [Chemical Formula 3-1]

[0072]

[0073] In the above chemical formula 3-1,

[0074] R 4 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and

[0075] Y is a group containing a methyl group, a vinyl group, or an alkoxysiloxy group having 1 to 4 carbon atoms, and

[0076] d is an integer from 2 to 500.

[0077] Specific examples of the above-mentioned dispersants include compounds of the following structural formulas, and may include one or more of these, but are not limited thereto.

[0078]

[0079]

[0080] The content of the above dispersant may be 0.1% by weight to 10% by weight based on the total weight of the thermally conductive silicone-based composition. If the content of the above dispersant exceeds 10% by weight based on the total weight of the thermally conductive silicone-based composition, the polar hydrophilic groups to be removed may increase due to the hydrophilic groups of the dispersant, causing stickiness of the composition, and if it is less than 0.1% by weight, adverse effects of aggregation may occur during the dispersion process.

[0081] The above-mentioned retardant can extend the pot life at room temperature and improve storage stability. The above-mentioned retardant may include alkyl alcohols such as 1-ethynylcyclohexan-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexin-3-ol, and 2-phenyl-3-butyn-2-ol; enyne compounds such as 3-methyl-3-pentene-1-phosphorus and 3,5-dimethyl-3-hexene-1-phosphorus; and methylalkenylsiloxane oligomers such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane. It may include one or more alkyloxysilanes such as dimethylbis(3-methyl-1-butyn-3-oxy)silane and methylvinylbis(3-methyl-1-butyn-3-oxy)silane; triaryl isocyanurate compounds, etc., but is not limited thereto.

[0082] The content of the above retardant may be 0.0001% to 5% by weight or 0.01% to 3% by weight based on the total weight of the thermally conductive silicone-based composition, but is not limited thereto.

[0083] The above adhesive agent may include one or more of epoxy-based organic compounds, acrylic-based organic compounds, vinyl-based organic compounds, and amine-based organic compounds.

[0084] Examples of the above epoxy-based organic compounds include silane compounds containing epoxy-based organic groups, such as glycidoxypropyltrimethoxysilane, glycidoxypropylethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxypropylmethyldimethoxysilane, epoxycyclohexylethyltrimethoxysilane, etc. Examples of the above acrylic-based organic compounds include silane compounds containing acrylic-based organic groups, such as methacryloxypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltriethoxysilane, acryloxypropyltrimethoxysilane, etc. Examples of the above vinyl organic compounds include vinyl organic group-containing silane compounds, such as triphenylvinylsilane, trismethoxyethoxyvinylsilane, triacetoxyvinylsilane, trimethylvinylsilane, triethylvinylsilane, vinyltrimethylsilane, tritrimethylsiloxyvinylsilane, trimethoxysilane, vinyltrimethoxysilane, etc. Examples of the above amine-based organic compounds include amine-based organic group-containing silane compounds, such as aminopropyltrimethylsiloxysilane, aminoethylaminopropyldimethoxymethylsilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropylmethyldiethoxysilane, aminopropylmethyldimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, diethylenetriaminopropyltrimethoxysilane, diethylenetriaminopropyltriethoxysilane, diethylenetriaminopropylmethyldimethoxysilane, diethylenetriaminopropylmethyldiethoxysilane, cyclohexylaminopropyltrimethoxysilane, hexanediaminomethyltrimethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltriethoxysilane, diethylaminomethyltriethoxysilane, diethylaminomethyldiethoxysilane, diethylaminomethyldiethoxysilane, methylaminopropyltrimethoxysilane, chlorodioxaphospholanooxide, etc.

[0085] The content of the adhesive promoter may be 0.05% to 5% by weight or 1% to 3% by weight based on the total weight of the silicone-based composition, but is not limited thereto. If the content of the adhesive promoter is less than 0.05% by weight, there may be a problem with reduced adhesive strength and reliability of the composition, and if it exceeds 5% by weight, there may be a problem with adhesion development and residual uncured material.

[0086] In one embodiment of the present invention, during a dispensing process using the thermally conductive silicon-based composition, the flow rate of the thermally conductive silicon-based composition may be 70 g / min or more, 75 g / min or more, or 80 g / min or more. Additionally, during a dispensing process using the thermally conductive silicon-based composition, the flow rate of the thermally conductive silicon-based composition may be 200 g / min or less, 180 g / min or less, or 150 g / min or less. A method for measuring the flow rate of the thermally conductive silicon-based composition is specifically described in the examples to be described later.

[0087] In the manufacturing of semiconductor packages, the size and shape of the pattern formed during the dispensing process of a thermally conductive silicon-based composition are critical. If the flow rate of the thermally conductive silicon-based composition does not fall within an appropriate range, the pattern may be non-uniform or fail to form the desired shape. More specifically, if the flow rate of the thermally conductive silicon-based composition is too high, excessive material may be dispensed, causing the pattern to spread or flow; if the flow rate is too low, the pattern may be broken or formed incompletely. Furthermore, since the dispenser moves at a constant speed, the amount of material discharged is determined by the flow rate. More specifically, if the flow rate of the thermally conductive silicon-based composition is too high, excessive material may be discharged, causing the pattern to become thick or spread; if the flow rate is too low, insufficient material may be supplied, resulting in the formation of an incomplete pattern. This directly affects the thickness and shape of the pattern. Additionally, when dispensing is performed at a constant speed, consistent quality results can be produced even when the process is repeated, provided the flow rate falls within an appropriate range. Forming consistent patterns increases process reliability and helps prevent quality issues that may occur later.

[0088] Accordingly, according to one embodiment of the present invention, the thermally conductive silicon-based composition may have a flow rate within an appropriate range, and accordingly, an appropriate discharge amount may be maintained during the dispensing process to form an accurate pattern, and the same quality may be exhibited even when the process is repeated.

[0089] Another embodiment of the present invention provides a cured product obtained by curing the thermally conductive silicon-based composition.

[0090] A cured article according to one embodiment of the present application may be formed using methods known in the art, except for curing the aforementioned thermally conductive silicon-based composition. More specifically, the thermally conductive silicon-based composition may be formed on a substrate using methods such as application, coating, printing, and curing, but is not limited thereto.

[0091] In addition, another embodiment of the present application provides an electronic device comprising the cured material.

[0092] A semiconductor package to which a thermally conductive silicon-based composition according to one embodiment of the present invention is applied is schematically illustrated in FIG. 1 below. FIG. 1 below shows a cross-sectional view of the semiconductor package, illustrating the application of TIM1 (Thermal Interface Material 1), a thermally conductive material according to the present invention, for thermal management purposes. This structure plays an important role in effectively dissipating heat generated from the semiconductor chip to maintain chip performance and prevent overheating.

[0093] More specifically, the chip in Fig. 1 below is a central processing unit or semiconductor device that generates heat during operation. The bump in Fig. 1 below is a solder bump (junction) that electrically and physically connects the chip to the package substrate and serves to transmit signals and power. The package substrate in Fig. 1 below is a basic structure that supports the chip and provides connections with external circuits. The heat spreader in Fig. 1 below is positioned on the chip to protect it and dissipate heat. The lid seal in Fig. 1 below is a sealing material that helps the lid securely adhere to the chip and the substrate, preventing contamination and aiding in heat management. TIM1 (Thermal Interface Material 1) in Fig. 1 below is a heat transfer material located between the chip and the heat spreader, which effectively dissipates heat by transferring the heat generated by the chip to the lid. The performance of this material is critical for heat management. The red arrow in Figure 1 below indicates the process in which heat generated from the chip is transferred to the heat spreader through TIM1, and the heat spreader releases that heat to the outside. This prevents the chip from overheating during operation.

[0094] According to one embodiment of the present invention, a thermally conductive silicon-based composition with improved dispersibility can be provided while maintaining high thermal conductivity and conventional mechanical properties.

[0095] Since the thermally conductive silicon-based composition according to one embodiment of the present invention has excellent flowability, it can be applied as a heat dissipation material in electronic components, such as various electronic devices, where excellent workability is required. In particular, the thermally conductive silicon-based composition according to one embodiment of the present invention can be more suitablely applied to TIM1 (Thermal Interface Material) in which lid attach is performed by applying a snap cure process.

[0096] The present specification will be explained in more detail below through examples. However, the following examples are intended only to illustrate the present specification and are not intended to limit the present specification.

[0097] <Example>

[0098] <Example 1>

[0099] Based on the total weight of the composition, 4.2 wt% of polydimethylsiloxane (viscosity at 23°C 0.35 Pa.s) having both ends of the molecular chain blocked by dimethylvinylsiloxy groups (viscosity at 23°C 0.01 Pa.s) having hydroxyl groups on both ends and side chains (number of hydrogen groups in one molecule is about 20) (molar ratio of hydrogen groups of polymethylhydrogensiloxane to vinyl groups of polydimethylsiloxane (H / Vi ratio) is 1.1), 0.01 wt% of a platinum tetravinyltetramethylcyclotetrasiloxane complex, 93.00 wt% of a filler (components of Table 1 below), 1.5 wt% of a dispersant of Formula 4 below, 0.06 wt% of a triaryl isocyanurate-based compound as a retardant, and 0.13 wt% of a vinyl-based organic compound as an adhesion promoter are mixed in a thin mixer A thermally conductive silicon-based composition was prepared by mixing. At this time, the mixture was mixed twice for 30 seconds each at 2,000 rpm at room temperature.

[0100] [Chemical Formula 4]

[0101]

[0102] <Examples 2–5 and Comparative Examples 1–8>

[0103] A thermally conductive silicon-based composition was prepared by performing the same procedure as Example 1 above, except that the type and content of the filler were adjusted as shown in Table 1 below.

[0104] [Table 1]

[0105]

[0106] Filler A: Spherical alumina with an average particle size of 45㎛

[0107] Filler B: Alumina with an average particle size of 3㎛ and a roundish shape

[0108] Filler C: Average particle size is 0.6 µm, and specific surface area is 6 m² 2 / g to 8 m 2 / g, spherical alumina

[0109] Filler D: Average particle size is 0.4㎛, and specific surface area is 6 m² 2 / g to 8 m 2 / g, spherical alumina

[0110] Filler E: Average particle size is 0.4㎛, and specific surface area is 5 m² 2 Alumina in the roundish form with less than / g

[0111] Filler F: Average particle size is 0.3㎛ and specific surface area is 5 m 2 Alumina in the roundish form with less than / g

[0112] Filler G: Average particle size is 0.2㎛ and specific surface area is 9 m 2 Spherical alumina exceeding / g

[0113] Filler H: Average particle size is 0.7㎛, and specific surface area is 5 m² 2 Alumina in the roundish form with less than / g

[0114] <Experimental Example>

[0115] The flow rate (g / min) of the thermally conductive silicon-based compositions prepared in the above examples and comparative examples was measured and is shown in Table 2 below.

[0116] <Flow-rate 측정방법>

[0117] The thermally conductive silicone-based composition of the above example or comparative example was placed in a 30CC syringe and degassed. Afterward, the amount of sample dispensed per 10 seconds using a pneumatic dispenser was recorded. This was repeated a total of 6 times to calculate the average value.

[0118] [Table 2]

[0119]

[0120] As shown in the results of Table 2 above, it can be confirmed that the thermally conductive silicon-based compositions of Examples 1 to 5 of the present invention have an appropriate flow rate value of 70 g / min or more, and accordingly, an appropriate discharge amount can be maintained during the dispensing process to form an accurate pattern, and the same quality can be exhibited even when the process is repeated.

[0121] However, as in the present invention, the average particle size is 0.1㎛ or more and less than 1㎛, and the specific surface area is 6 m² 2 / g to 8 m 2 It can be confirmed that the thermally conductive silicon-based compositions of Comparative Examples 1 to 4 and 8, which do not contain the first alumina of g / g, have a flow rate value of 62 g / min or less. In addition, it can be confirmed that the thermally conductive silicon-based compositions of Comparative Examples 5 to 7, which do not satisfy the content range of the first alumina (5 wt% to 25 wt%) as in the present invention even when containing the first alumina as in the present invention, also have a very low flow rate value.

[0122] Accordingly, since the thermally conductive silicon-based composition according to one embodiment of the present invention has excellent flowability, it can be applied as a heat dissipation material in electronic components, such as various electronic devices, where excellent workability is required. In particular, the thermally conductive silicon-based composition according to one embodiment of the present invention can be more suitablely applied to TIM1 (Thermal Interface Material 1) in which a lid attach is performed by applying a snap cure process.

Claims

1. 1) A first polysiloxane comprising at least one alkenyl group; 2) A second polysiloxane comprising at least one hydrogen group; 3) Hydrosilylation catalyst; and 4) Includes filler, The above filler has an average particle size of 0.1㎛ or more and less than 1㎛, and a specific surface area of ​​6 m² 2 / g to 8 m 2 It includes a first alumina of / g, A thermally conductive silicon-based composition having a content of 5% to 25% by weight of the first alumina based on the total weight of the above filler.

2. A thermally conductive silicone-based composition according to claim 1, wherein the first polysiloxane is represented by the following chemical formula 1: [Chemical Formula 1] (R 1a R 2a R 3a SiO 1 / 2 ) aa (R 4a R 5a SiO 2 / 2 ) ba (R 6a SiO 3 / 2 ) ca (SiO 4 / 2 ) da In the above chemical formula 1, R 1a to R 6a At least one of them is an alkenyl group, and The remainders are identical or different from one another, each independently an alkyl group, an alkoxy group, an aryl group, or a silanol group, which are substituted or unsubstituted with a halogen, and aa + ba + ca + da = 1, 0 ≤ aa < 1, 0 ≤ ba < 1, 0 ≤ ca < 1, 0 ≤ da < 1 is satisfied.

3. A thermally conductive silicone-based composition according to claim 1, wherein the second polysiloxane is represented by the following chemical formula 2: [Chemical Formula 2] (R 1b R 2b R 3b SiO 1 / 2 ) ab (R 4b R 5b SiO 2 / 2 ) bb (R 6b SiO 3 / 2 ) cb (SiO 4 / 2 ) db In the above chemical formula 2, R 1b to R 6b At least one of them is a hydrogen group, and The remainders are identical or different from one another, each independently an alkyl group, an alkoxy group, an aryl group, or a silanol group, which are substituted or unsubstituted with a halogen, and ab + bb + cb + db = 1, 0 ≤ ab < 1, 0 ≤ bb < 1, 0 ≤ cb < 1, 0 ≤ db < 1 is satisfied.

4. A thermally conductive silicon-based composition according to claim 1, wherein the hydrosilylation catalyst comprises one or more of a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst.

5. A thermally conductive silicon-based composition according to claim 1, wherein the filler further comprises one or more of a second filler having an average particle size of 1 μm or more and less than 10 μm, and a third filler having an average particle size of 10 μm or more and less than 100 μm.

6. A thermally conductive silicon-based composition according to claim 1, wherein the filler further comprises a second alumina having an average particle size of 1 μm or more and less than 10 μm, and a third alumina having an average particle size of 10 μm or more and less than 100 μm.

7. In Claim 1, based on the total weight of the thermally conductive silicon-based composition, A thermally conductive silicone-based composition having a content of the first polysiloxane of 0.1 wt% to 10 wt%, a content of the second polysiloxane of 0.1 wt% to 10 wt%, a content of the hydrosilylation catalyst of 0.0001 wt% to 0.1 wt%, and a content of the filler of 80 wt% to 98 wt%.

8. A thermally conductive silicone-based composition according to claim 1, wherein the silicone-based composition further comprises one or more of a dispersant, a retardant, and an adhesion promoter.

9. A thermally conductive silicon-based composition according to claim 8, wherein the dispersant is represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, R 1 It is a group containing an alkoxysiloxy group having 1 to 4 carbon atoms, and R 2 is a siloxane represented by the following chemical formula 3-1, or a monovalent hydrocarbon group having 6 to 18 carbon atoms, and X is each independently a divalent hydrocarbon group having 2 to 10 carbon atoms, and R 3 Each is independently hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a and b are each independently integers greater than or equal to 1, c is an integer greater than or equal to 0, and (a+b+c) is an integer greater than or equal to 4, and [Chemical Formula 3-1] In the above chemical formula 3-1, R 4 is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and Y is a group containing a methyl group, a vinyl group, or an alkoxysiloxy group having 1 to 4 carbon atoms, and d is an integer from 2 to 500.

10. A thermally conductive silicone-based composition according to claim 8, wherein the retardant comprises one or more of alkyl alcohols, enyne compounds, methyl alkenylsiloxane oligomers, alkyloxysilanes, and triaryl isocyanurate-based compounds.

11. A cured product obtained by curing a thermally conductive silicon-based composition of any one of claims 1 to 10.

12. An electronic device comprising the cured product of claim 11.

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