Thermally conductive composition
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-07-02
- Publication Date
- 2026-08-14
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Figure 2026527464000001_ABST
Abstract
Description
[Technical Field]
[0001] Background technology In recent years, efficient methods for bonding silicone rubber to incompatible materials such as organic resins have been reported. For example, U.S. Patent No. 6,887,932 discloses the preparation and use of cyclic polymethylhydrogensiloxanes containing mono-, di-, or triphenylene skeletons that are not directly bonded to silicon atoms. Examples of such compounds include BPA derivatives bonded to terminal cyclic polymethylhydrogensiloxane groups via propoxyl linkage groups, as shown below:
[0002] [ka] (In the formula, n is between 1 and 4).
[0003] Unfortunately, when preparing such an adhesion promoter, one D H A considerable amount of the following by-products, which are terminated with only four units, are formed.
[0004] [ka]
[0005] Furthermore, the preparation of such adhesion promoters requires the use of a Pt catalyst, which is difficult to remove and thus negatively affects the shelf life of the part B addition-curing formulation. Therefore, there is a need to find a reactive adhesion promoter that can be prepared in high yield and high purity without using a Pt catalyst. [Overview of the project]
[0006] In one aspect, the present invention is a composition, a) Compound of formula (1)
[0007] [ka] (wherein n is 1, 2, or 3) b) Divinyl-terminated poly(di-C1~C6-alkyl)siloxanes, c) Organohydrogenpolysiloxane and, d) Thermally conductive filler particles, e) A first filler treatment agent which is a trimethoxysilyl-terminated polydimethylsiloxane, f)C6~C 20 -A second packing agent which is alkyltrimethoxysilane, g) Platinum catalyst and, The present invention addresses the needs in the art by providing a composition containing the present invention.
[0008] The composition of the present invention is useful as a thermally conductive material. [Modes for carrying out the invention]
[0009] The present invention is a composition, a) Compound of formula (1)
[0010] [ka] (wherein n is 1, 2, or 3) b) Divinyl-terminated poly(di-C1~C6-alkyl)siloxanes, c) Organohydrogenpolysiloxane and, d) Thermally conductive filler particles, e) A first filler treatment agent which is a trimethoxysilyl-terminated polydimethylsiloxane, f)C6~C 20 -A second packing agent which is alkyltrimethoxysilane, g) Platinum catalyst and, It is a composition containing [the specified ingredient].
[0011] The compound of Formula 1 can be prepared in a single step by dehydrogenative condensation of bisphenol A and a cyclic polymethylhydrogensiloxane of Formula 2 in the presence of a catalytic amount of a Lewis acid catalyst, such as tris(pentafluorophenyl)borane (BCF).
[0012]
Chemical formula
[0013] The temperature of the reaction is preferably controlled in the range of 20 °C to 40 °C. The BCF catalyst can be easily removed by treatment with Al2O3 or can be completely deactivated at 100 °C for 10 minutes. The compounds of the present invention do not require a platinum catalyst, which is a great advantage for the reasons described above.
[0014] Preferably, the divinyl-terminated poly(di-C1-C6-alkyl)siloxane is a divinyl-terminated polydimethylsiloxane having a degree of polymerization (dp) in the range from 8, or from 20, or from 100 to 600, or up to 300. The organohydrogenpolysiloxane (Si-H-containing polysiloxane) preferably has a dp in the range of 10 to 100. The thermally conductive filler particles are preferably alumina or zinc oxide particles. The trimethoxysilyl-terminated polydimethylsiloxane (PDMS) filler treatment agent preferably has a dp in the range of 10 to 150. C6-C 20 An example of a second filler treatment agent which is a C6-C-alkyltrimethoxysilane is n-decyltrimethoxysilane. An example of a platinum catalyst is a platinum 85 catalyst.
[0015] [[ID=ID=22]]The composition may further contain an inhibitor of a platinum catalyst, such as phenylbutynol, and a pigment, such as STAN-TONE 40SP03 Blue pigment.
[0016] The concentration of the thermally conductive filler particles is preferably in the range of 1000 or 1200 pbw to 1600 or ~1450 pbw per 100 parts by weight (pbw) of divinyl-terminated poly(di-C1~C6-alkyl)siloxane. The thermally conductive filler particles preferably have a multimodal distribution in the ranges of 200 nm to 800 nm, 1 μm to 10 μm, and 20 μm to 100 μm when measured by laser diffraction. 50 The particles present in the composition are alumina or zinc oxide particles having a specific particle size, or both.
[0017] The concentrations of the first and second filler treatment agents are preferably in the range of 0.5 to 3 pbw per 100 pbw of thermally conductive filler particles. The ratio of Si-H groups in the organohydrogenpolysiloxane to vinyl groups in the divinyl-terminated poly(di-C1-C6-alkyl)siloxane is preferably in the range of 0.5:1 to 1.1:1, and the concentration of the ratio of Si-H groups in the organohydrogenpolysiloxane to Si-H groups in the compound of formula 1 is preferably in the range of 0.1:1 to 1:1. [Examples]
[0018] Intermediate Example 1 - Preparation of compound (n=1) of formula 1
[0019] [ka]
[0020] Bisphenol A (BPA, 100.3g), anhydrous toluene (295.2g, ACS grade), heptane (77.0g), and 809g of D H 4 (809g, available from Gelest) was placed in a 2L flask. The solvent was distilled, and anhydrous toluene (160.0g) was added back into the flask and returned to (D HResidual water (from 4) was removed. The mixture was stirred overnight, and tris(pentafluorophenyl)borane / toluene catalyst (4.46% BCF 248 μL) was added to the flask. The pot temperature was controlled in the range of 22 °C to 38 °C using a heating block cooled with dry ice, and stirring was continued for 3 hours and 50 minutes. Then, Al2O3 (23 g) was added to the flask to remove BCF. Stirring was continued for an additional 1.5 hours, and then the contents of the flask were filtered through a 0.45 μm membrane. Residual volatiles were removed at 1 torr and 60 °C for 50 minutes to obtain the desired product (278.0 g). 1 H, 13 C, and 29 The structure was confirmed by H, C, and Si NMR spectroscopy.
[0021] Preparation of Intermediate Example 2 - Compounds of Formula 1 (n = 1, 2, and 3)
[0022] [Chemical formula]
[0023] BPA (104.3 g), anhydrous toluene (494.5 g, ACS grade), and DOWSIL™ MH-1109 Fluid (791.2 g, a trademark of The Dow Chemical Company or its affiliates) were charged into a 2 L flask equipped with a thermocouple, a mechanical stirrer, and an adapter to a N2 bubbler. The headspace of the flask was purged with N2 for 5 minutes, and then BCF / toluene catalyst (4.46% BCF 199 μL) was added to the flask. The pot temperature was controlled in the range of 22 °C to 30 °C using a heating block cooled with dry ice. Gas evolved during this time, and when the evolution subsided, an additional amount of BCF / toluene catalyst (57 μL) was added, and this was repeated 5 times. The contents of the flask were stirred for an additional 3 hours, and then Al2O3 (47 g) was added. Stirring was continued for an additional 2 hours, and then the contents of the flask were filtered through a 0.45 μm membrane. Residual volatiles were removed at 1 torr and 60 °C for 50 minutes to obtain the desired product (438.6 g). 1 H, 13 C, and 29The structure was confirmed by Si NMR spectroscopy.
[0024] Example 1 - Preparation of thermally conductive compounds Vinyl-terminated polydimethylsiloxane (60 mPa·s, 6.5 pbw), trimethoxysiloxy-terminated polydimethylsiloxane (dp=30; 0.7 pbw), and n-decyltrimethoxysilane (0.2 pbw) were placed in a 1 L planetary mixer, followed by the addition of AES-12 alumina (18.8 pbw) and AL-M734 alumina (20.8 pbw). The mixture was stirred at room temperature for 10 minutes, after which DAM-40K alumina particles (25 pbw) were added. Stirring was continued for another 10 minutes, during which an additional amount of DAM-40K alumina particles (25 pbw) was added. Stirring was continued for another 10 minutes, followed by scraping, and the mixture was further mixed for an additional 10 minutes. The contents were heated at 160°C under vacuum for 60 minutes, and then cooled to room temperature over 30 minutes. STAN-TONE 40SP03 Blue (0.2 pbw), SiH-terminated polyorganosiloxane (dp=14, 2.62 pbw), the compound of Formula 1 from Example 2 (0.06 pbw), and phenylbutynol (0.01 pbw) were added to a mixer and mixed for 15 minutes, then scraped off and mixed further under vacuum for an additional 15 minutes. The contents of the mixer were removed, and then platinum 85 catalyst (0.1 pbw, 6000 ppm Pt) was added to the mixture.
[0025] Measurement of hardness A mold with plate dimensions of 120mm x 120mm x 2mm was used, with PTFE sheets placed between each plate of the mold. The composition was placed inside the mold to form a sheet with a thickness of 2mm, which was then cured by hot pressing at 120°C for 60 minutes. After that, the JIS Type A hardness was measured using a JIS Type A hardness tester. Hardness was measured by stacking three sheets. Furthermore, the hardness of each thermally conductive component was measured again after aging at 200°C for 72 hours.
[0026] Thermal conductivity (Hot Disk) In a mold with plate dimensions of 50 mm × 30 mm × 6 mm, test specimens of thermally conductive samples were prepared with PTFE sheets between each plate of the mold. Each composition was placed in the mold to form a sheet with a thickness of 6 mm, which was then cured by hot pressing at 120°C for 60 minutes. The sheets were removed from the mold and stored at 25°C for 24 hours. Subsequently, the thermal conductivity of two samples was measured and averaged using a Hot Disk TPS 500S manufactured by Hot Disk AB (Goteborg, Sweden).
[0027] Wrap shear strength and cohesive failure rate First, the adhesive strength (MPa) and cohesive failure rate (%) of each thermally conductive component were measured by cleaning the aluminum die-cast substrate (ADC12) with isopropyl alcohol. The composition was filled into an overlapping region defined by the aluminum die-cast substrate, which had dimensions of 10 mm × 24 mm × 1 mm. The composition was cured by hot pressing at 120°C for 60 minutes while placed in the overlapping region defined by the substrate. After curing, excess curing product was removed from around the overlapping region using a cutter, and the properties were measured by tensile testing at a measurement speed of 50 mm / min.
[0028] Table 1 summarizes the hardness, adhesive strength, and cohesive failure rate of the composition of Example 3.
[0029] [Table 1]
Claims
1. A composition, a) Compound of formula (1) 【Chemistry 1】 (wherein n is 1, 2, or 3) b) Divinyl-terminated poly(G-C) １ ~C ６ -Alkyl)siloxane, c) Organohydrogenpolysiloxane and d) Conductive filler particles and e) A first filler treatment agent which is a trimethoxysilyl-terminated polydimethylsiloxane, f) C ６ ~C ２０ - A second packing agent which is alkyltrimethoxysilane, g) Platinum catalyst and, A composition containing the following:
2. The aforementioned divinyl-terminated poly(di-C) １ ~C ６ The composition according to claim 1, wherein the alkyl)siloxane has a degree of polymerization in the range of 8 to 600, the organohydrogenpolysiloxane has a degree of polymerization in the range of 10 to 100, the thermally conductive filler particles are alumina or zinc oxide particles, or a combination thereof, and the first filler treatment agent has a degree of polymerization in the range of 10 to 150.
3. The concentration of the thermally conductive filler particles is in the range of 1000 to 1500 parts by weight per 100 parts by weight of the poly(di-C １ -C ６ -alkyl) siloxane, and the concentrations of the first filler treatment agent and the second filler treatment agent are in the range of 0.5 to 3 parts by weight per 100 parts by weight of one or more thermally conductive fillers. The ratio of the Si-H groups in the organohydrogenpolysiloxane to the vinyl groups of the divinyl-terminated poly(di-C １ -C ６ -alkyl) siloxane is in the range of 0.5:1 to 1.1:1, and the ratio of the concentration of the Si-H groups in the organohydrogenpolysiloxane to the Si-H groups in the compound of Formula 1 is in the range of 0.1:1 to 1:
1. The thermally conductive filler particles are alumina particles. The composition according to claim 2.
4. Divinyl-terminated poly(G-C) １ ~C ６ The (-alkyl)siloxane has a degree of polymerization in the range of 20 to 300, and the concentration of the thermally conductive filler particles is the poly(di-C) １ ~C ６ The composition according to claim 3, wherein the amount is in the range of 1200 to 1450 parts by weight per 100 parts by weight of alkyl)siloxane.
5. The aforementioned divinyl-terminated poly(di-C) １ ~C ６ The composition according to claim 4, wherein the alkyl)siloxane is a divinyl-terminated polydimethylsiloxane.
6. The composition according to claim 5, further comprising the platinum catalyst inhibitor and the pigment.
7. The composition according to claim 6, wherein the inhibitor of the platinum catalyst is phenylbutynol.