Patent Application
20250019585
The present invention relates to heat-conducting silicone compositions, and to the production and use thereof.
Heat-conducting silicone compositions find wide use for heat management in the automobile and electronics industries. Examples of important presentation forms include heat-conducting adhesives, heat-conducting pads, gap fillers and encapsulation compounds. Of the applications mentioned, gap fillers for lithium ion batteries of electrical vehicles are by far the greatest application in terms of volume. Gap fillers are heat-conducting elastomers that completely and sustainably fill air gaps caused by manufacturing tolerances, differences in build height or different coefficients of expansion, and minimize thermal resistance, for example between electronic components and cooling jackets or heatsinks.
The state of the art includes different thermally conductive fillers that are added to the silicone to increase its thermal conductivity. However, these have serious disadvantages. Ceramic fillers, for example alumina, have a very high density and hence increase the weight of the components very significantly. Moreover, they are comparatively costly. Many thermally conductive metallic fillers, for example finely divided copper and silver particles, are likewise unsuitable for gap fillers on account of their high density and cost.
Many further fillers of high thermal conductivity, for example carbon nanotubes, boron nitride and aluminum nitride, on account of their comparatively high costs, can also be used only to a limited degree, or in small amounts or in specific applications.
The prior art includes various heat-conducting silicone compositions containing aluminum particles as heat-conducting filler. These are comparatively light and inexpensive. Moreover, aluminum, being a semiconductor, has extremely low electrical conductivity. However, the aluminum particles according to the prior art are unsuitable for use as gap filler in lithium ion batteries for electrical vehicles:
Very finely divided aluminum particles having an average particle size below 20 μm are used in the prior art. The use of aluminum particles smaller than 20 μm is disadvantageous since such particles have comparatively low minimum ignition energy and hence present a risk of dust explosion and entail complex and costly safety precautions in industrial processing. Moreover, gap fillers containing such finely divided aluminum particles do not achieve the requisite fire characteristics according to UL94 V-0.
Another disadvantage of very fine aluminum particles or ground aluminum particles is that such particles have a comparatively high surface area and bind a very large amount of polymer. This increases the viscosity of the silicone composition very significantly, such that it is only possible to produce mixtures having comparatively low filler levels and low thermal conductivity. In the case of higher filler levels, the composition becomes very stiff and can no longer be processed by conventional methods, for example dispensers. It is also found that silicone compositions containing ground aluminum particles are comparatively highly combustible.
There are numerous patent specifications that disclose the use of finely divided aluminum particles in thermally conductive silicone compositions, for example in US2007167564, US2002014692, US2003049466, US2018022977, JP2014037460, WO21079714, US2011163460, US2016208156, JP2010013521, JP2014037460, US2016060462 and US2016068732. None of these documents contains disclosures as to the shape of the particles, and there is merely a very broad definition of average particle diameters. The specific examples disclose the use of very fine aluminum particles <20 μm.
However, this use of very small aluminum particles <20 μm is associated with a major drawback. Since they have comparatively low minimum ignition energy and hence present a risk of dust explosion and they entail complex and costly safety precautions in industrial processing. Moreover, silicone compositions which such finely divided aluminum particles do not achieve the required fire characteristics according to UL94 V-0 and are consequently unsuitable for use as a gap filler in lithium ion batteries. An additional drawback is that such finely divided aluminum particles have a large surface area and bind a very large amount of polymer. This increases the viscosity of the silicone composition very significantly. It is only possible to produce mixtures having comparatively low filler levels and low thermal conductivity.
US2017002248 claims thermal interface materials having a high thermal conductivity of >6 W/mK and a low secant modulus of elasticity. A broad selection of possible matrix materials is specified (thermoplastics, thermosets, polymers). A broad selection of possible thermally conductive fillers is disclosed, for example metal oxides, metal nitrides or ceramics, including metallic aluminum, without any further specification of shape and size. The examples disclose, as matrix materials, addition-crosslinking silicone composition, silicone oil and mineral oil, and, as filler, exclusively combinations of alumina and metallic aluminum, by in each case mixing three types of alumina of different size and four types of aluminum (Al-1: 150 μm, Al-2: 80 μm, Al-3: 5 μm, Al-4: 50 μm of different size, all types being spherical. The content of aluminum particles here is greater than 42% by weight, and the content of alumina particles greater than 37% by weight. The proportion of added small aluminum particles <20 μm (particles of example Al-3) based on the total amount of aluminum particles is greater than 20% in each case. The addition and content of very small aluminum particles <20 μm is associated with the disadvantages mentioned. The use of such large amounts of alumina additionally makes such thermal interface materials very costly to manufacture, and causes them to have a comparatively high density of greater than 2.69 g/ml.
It was therefore an object of the present invention to provide heat-conducting silicone elastomer compositions that do not show the abovementioned disadvantages of the prior art, and which combine the properties of low density, low costs and high thermal conductivity.
This object is achieved by the inventive crosslinkable heat-conducting silicone compositions (Y) which contain comparatively large aluminum particles having an average particle size of 20 to 150 mm, of predominantly rounded surface shape, and which simultaneously have a particularly large or broad particle distribution range. Completely surprisingly, it was found in experiments that these inventive silicone compositions (Y) have distinctly reduced combustibility.
In the context of the present invention, aluminum particles having a “predominantly rounded surface shape” are understood to mean those having a spherical to oval, irregular or else nodular shape, with simultaneously smooth and curved surfaces.
Noninventive aluminum particle shapes are shown by way of example by
Inventive metallic aluminum particles having predominantly rounded surface shape are therefore neither angular nor spiky. However, they may contain such particles to the extent of an impurity without any disruption of their inventive action.
The present invention thus provides a crosslinkable, heat-conducting silicone composition (Y) comprising
In the context of this invention, the terms “heat-conducting” and “thermally conductive” are equivalent.
Thermally conductive fillers (Z) in the context of this invention are understood to mean any fillers having a thermal conductivity of at least 5 W/mK.
A heat-conducting silicone composition (Y) in the context of this invention is understood to mean those silicone composition that distinctly surpass the thermal conductivity of a filler- and additive-free polydimethylsiloxane, typically about 0.2 W/mK, characterized in that they have a thermal conductivity of at least 0.6 W/mK.
In the context of this invention, all parameters that describe particle size (parameter: median diameter x50) or particle size distribution (parameter: distribution range SPAN) are based on a volume-based distribution. The indices mentioned may be determined, for example, by means of dynamic image analysis according to ISO 13322-2 and ISO 9276-6, for example with a Camsizer X2 from Retsch Technology.
In order not to create an excessive number of pages in the description of the present invention, only the preferred embodiments of the individual features are detailed in the description.
However, the expert reader will explicitly understand this manner of disclosure such that any combination of different levels of preference is thus also explicitly disclosed and explicitly desired.
As crosslinkable silicone composition (S), it is possible to use silicones known to the person skilled in the art from the prior art, such as addition-crosslinking, peroxide-crosslinking, condensation-crosslinking or radiation-crosslinking silicone compositions (S). Preference is given to using addition-crosslinking or peroxide-crosslinking silicone compositions (S).
Peroxide-crosslinking silicone compositions (S) have long been known to the person skilled in the art. In the simplest case, they contain at least one organopolysiloxane having at least 2 crosslinkable groups per molecule, for example methyl or vinyl groups, and at least one suitable organic peroxide catalyst. If the compositions of the invention are crosslinked by means of free radicals, crosslinking agents used are organic peroxides that serve as a source of free radicals. Examples of organic peroxides are acyl peroxides, such as dibenzoyl peroxide, bis(4-chlorobenzoyl) peroxide, bis(2,4-dichlorobenzoyl) peroxide and bis(4-methylbenzoyl) peroxide; alkyl peroxides and aryl peroxides, such as di-tert-butyl peroxide, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, dicumyl peroxide and 1,3-bis(tert-butylperoxyisopropyl)benzene; perketals, such as 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane; peresters, such as diacetyl peroxydicarbonate, tert-butyl perbenzoate, tert-butyl peroxy-isopropylcarbonate, tert-butyl peroxyisononanoate, dicyclohexyl peroxydicarbonate and 2,5-dimethylhexane 2,5-diperbenzoate.
It is possible to use one kind of organic peroxide; it is also possible to use a mixture of at least two different kinds of organic peroxide.
Particular preference is given to using addition-crosslinking silicone compositions (S).
Addition-crosslinking silicone compositions(S) used in accordance with the invention are known in the prior art and in the simplest case contain
The addition-crosslinking silicone compositions (S) may be one-component silicone compositions or else two-component silicone compositions.
In two-component silicone compositions (S), the two components of the addition-crosslinking silicone compositions (S) of the invention may contain any constituents in any combination, generally with the proviso that one component does not simultaneously contain siloxanes having an aliphatic multiple bond, siloxanes with Si-bonded hydrogen and catalyst, i.e. essentially does not simultaneously contain constituents (A), (B) and (D), or (C) and (D).
As is well known, the compounds (A) and (B) or (C) that are used in the addition-crosslinking silicone compositions (S) of the invention are chosen such that crosslinking is possible. For example, compound (A) has at least two aliphatically unsaturated radicals and (B) at least three Si-bonded hydrogen atoms, or compound (A) has at least three aliphatically unsaturated radicals and siloxane (B) at least two Si-bonded hydrogen atoms, or else, rather than compound (A) and (B), siloxane (C) having aliphatically unsaturated radicals and Si-bonded hydrogen atoms in the abovementioned ratios is used. Also are mixtures of (A) and (B) and (C) having the abovementioned ratios of aliphatically unsaturated radicals and Si-bonded hydrogen atoms.
The addition-crosslinking silicone composition (S) of the invention typically contains 30-99.0% by weight, preferably 40-95% by weight and more preferably 50-90% by weight of (A). The addition-crosslinking silicone composition (S) of the invention typically contains 1-70% by weight, preferably 3-50% by weight and more preferably 8-40% by weight (B). If the addition-crosslinking silicone composition of the invention contains component (C), typically at least 30% by weight, preferably at least 45% by weight, more preferably at least 58% by weight (C), based on the total amount of addition-crosslinking silicone composition (S) of the invention is present.
The compound (A) used in accordance with the invention may comprise silicon-free organic compounds having preferably at least two aliphatically unsaturated groups, and organosilicon compounds having at least two aliphatically unsaturated groups, or else mixtures thereof.
Examples of silicon-free organic compounds (A) are 1,3,5-trivinylcyclohexane, 2,3-dimethyl-1,3-butadiene, 7-methyl-3-methylene-1,6-octadiene, 2-methyl-1,3-butadiene, 1,5-hexadiene, 1,7-octadiene, 4,7-methylene-4,7,8,9-tetrahydroindene, methylcyclopentadiene, 5-vinyl-2-norbornene, bicyclo[2.2.1]hepta-2,5-diene, 1,3-diisopropenylbenzene, polybutadiene containing vinyl groups, 1,4-divinylcyclohexane, 1,3,5-triallylbenzene, 1,3,5-trivinylbenzene, 1,2,4-trivinylcyclohexane, 1,3,5-triisopropenylbenzene, 1,4-divinylbenzene, 3-methyl-1,5-heptadiene, 3-phenyl-1,5-hexadiene, 3-vinyl-1,5-hexadiene and 4,5-dimethyl-4,5-diethyl-1,7-octadiene, N,N′-methylenebisacrylamide, 1,1,1-tris(hydroxymethyl)propane triacrylate, 1,1,1-tris(hydroxymethyl)propane trimethacrylate, tripropylene glycol diacrylate, diallyl ether, diallylamine, diallyl carbonate, N,N′-diallylurea, triallylamine, tris(2-methylallyl)amine, 2,4,6-triallyloxy-1,3,5-triazine, triallyl-s-triazine-2,4,6(1H,3H,5H)-trione, diallyl malonate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, poly(propylene glycol) methacrylate.
The addition-crosslinking silicone compositions (S) of the invention preferably contain, as constituent (A), at least one aliphatically unsaturated organosilicon compound, it being possible to use any of the aliphatically unsaturated organosilicon compounds used to date in addition-crosslinking compositions, for example silicone block copolymers having urea segments, silicone block copolymers having amide segments and/or imide segments and/or ester amide segments and/or polystyrene segments and/or silarylene segments and/or carborane segments and silicone graft copolymers having ether groups.
Organosilicon compounds (A) used that have SiC-bonded radicals having aliphatic carbon-carbon multiple bonds are preferably linear or branched organopolysiloxanes composed of units of the general formula (I)
R4aR5bSiO(4-a-b)/2 (I)
R4 radical may be a mono- or polyvalent radical, where the polyvalent radicals, for example bivalent, trivalent and tetravalent radicals, may then connect multiple, for instance two, three or four, siloxy units of the formula (I) to one another.
Further examples of R4 are the monovalent radicals —F, —Cl, —Br, OR6, —CN, —SCN, —NCO and SiC-bonded, substituted or unsubstituted hydrocarbyl radicals, which may be interrupted by oxygen atoms or the —C(O)— group, and divalent radicals Si-bonded at either end as per formula (I). If R4 radical comprises SiC-bonded substituted hydrocarbyl radicals, preferred substituents are halogen atoms, phosphorus-containing radicals, cyano radicals, —OR6, —NR6—, —NR62, —NR6—C(O)—NR62, —C(O)—NR62, —C(O)R6, —C(O) OR6, —SO2-Ph and —C6F5. R6 here is independently the same or different and is a hydrogen atom or a monovalent hydrocarbyl radical having 1 to 20 carbon atoms and Ph is the phenyl radical.
Examples of R4 radicals are alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobulyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical, and isooctyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical, cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical, alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.
Examples of substituted R4 radicals are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2′,2′,2′-hexafluoroisopropyl radical, the heptafluoroisopropyl radical, haloaryl radicals, such as the o-, m- and p-chlorophenyl radical, —(CH2)—N(R6)C(O)NR62, —(CH2)o—C(O)NR62, —(CH2)o—C(O)R6, —(CH2)o—C(O)OR6, —(CH2)o—C(O)NR62, —(CH2)—C(O)—(CH2)pC(O) CH3, —(CH2)—O—CO—R6, —(CH2)—NR6— (CH2)p—NR62, (CH2)o—O— (CH2)pCH(OH) CH2OH, —(CH2)o(OCH2CH2)pOR6, —(CH2)o—SO2-Ph and —(CH2)o—O—C6F5, where R6 and Ph conforms to the definition given above and o and p are identical or different integers from 0 to 10.
Examples of R4 as divalent radicals Si-bonded at either end as per formula (I) are those that derive from the monovalent examples given above for R4 radical in that there is an additional bond through substitution of a hydrogen atom; examples of such radicals are —(CH2)—, —CH(CH3)—, —C(CH3)2—, —CH(CH3)—CH2—, —C6H4—, —CH(Ph)—CH2—, —C(CF3)2—, —(CH2)o—C6H4—(CH2)o—, —(CH2)o—C6H4—C6H4— (CH2)o—, —(CH2O)p, (CH2CH2O)o, —(CH2)o—Ox—C6H4—SO2—C6H4—Ox— (CH2)o—, where x is 0 or 1, and Ph, o and p have the definition given above.
R4 radical is preferably a monovalent SiC-bonded, optionally substituted hydrocarbyl radical which is free of aliphatic carbon-carbon multiple bonds and has 1 to 18 carbon atoms, more preferably a monovalent SiC-bonded, hydrocarbyl radical which is free of aliphatic carbon-carbon multiple bonds and has 1 to 6 carbon atoms, especially the methyl or phenyl radical.
R5 radical may be any groups amenable to an addition reaction (hydrosilylation) with an SiH-functional compound.
If R5 radical comprises SiC-bonded, substituted hydrocarbyl radicals, preferred substituents are halogen atoms, cyano radicals and —OR6 where R6 has the definition given above.
R5 radical preferably comprises alkenyl and alkynyl groups having 2 to 16 carbon atoms, such as vinyl, allyl, methallyl, 1-propenyl, 5-hexenyl, ethynyl, butadienyl, hexadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, vinylcyclohexylethyl, divinylcyclohexylethyl, norbornenyl, vinylphenyl and styryl radicals, particular preference being given to using vinyl, allyl and hexenyl radicals.
The molecular weight of constituent (A) may vary within wide limits, for instance between 102 and 106 g/mol. For example, constituent (A) may be an alkenyl-functional oligosiloxane of relatively low molecular weight, such as 1,2-divinyltetramethyldisiloxane, but also a high-polymeric polydimethylsiloxane having Si-bonded vinyl groups in chain or terminal positions, for example having a molecular weight of 105 g/mol (number average determined by means of NMR). Nor is the structure of the molecules that form constituent (A) fixed; more particularly, the structure of a macromolecular, i.e. oligomeric or polymeric, siloxane may be linear, cyclic, branched or else resinous and network-like. Linear and cyclic polysiloxanes are preferably composed of units of the formula R43SiO1/2, R5R42SiO1/2, R5R4SiO1/2 and R42SiO2/2, where R4 and R5 have the definition given above. Branched and network-like polysiloxanes additionally contain trifunctional and/or tetrafunctional units, preference being given to those of the formulae R4SiO3/2, R5SiO3/2 and SiO4/2. It is of course also possible to use mixtures of different siloxanes that meet the criteria of constituent (A).
Particularly preferred as component (A) is the use of vinyl-functional, essentially linear polydiorganosiloxanes having a viscosity of 10 to 100 000 mPa·s, more preferably of 15 to 20 000 mPa·s, especially preferably 20 to 2000 mPa·s, in each case at 25° C.
As organosilicon compound (B), it is possible to use any hydrogen-functional organosilicon compounds that have also been used to date in addition-crosslinkable compositions.
Organopolysiloxanes (B) having Si-bonded atoms that are used are preferably linear, cyclic or branched organopolysiloxanes composed of units of the general formula (III)
R4cHdSiO(4-c-d)/2 (III)
The organopolysiloxane (B) used in accordance with the invention preferably contains Si-bonded hydrogen in the range from 0.01 to 1.7 percent by weight (% by weight), based on the total weight of the organopolysiloxane (B). Preferably in the range of 0.02-0.8% by weight, more preferably in the range of 0.03-0.3% by weight.
The molecular weight of constituent (B) may likewise vary within wide limits, for instance between 102 and 106 g/mol. For example, constituent (B) may be an SiH-functional oligosiloxane of relatively low molecular weight, such as tetramethyldisiloxane, but also a high-polymeric polydimethylsiloxane having SiH groups in chain or terminal positions or a silicone resin having SiH groups.
Nor is the structure of the molecules that form constituent (B) fixed; more particularly, the structure of a macromolecular, i.e. oligomeric or polymeric, SiH-containing siloxane may be linear, cyclic, branched or else resinous and network-like. Linear and cyclic polysiloxanes (B) are preferably composed of units of the formula R43SiO1/2, HR42SiO1/2, HR4SiO2/2 and R42SiO2/2, where R4 has the definition given above. Branched and network-like polysiloxanes additionally contain trifunctional and/or tetrafunctional units, preference being given to those of the formulae R4SiO3/2, HSiO3/2 and SiO4/2, where R4 has the definition given above.
It is of course also possible to use mixtures of different siloxanes that meet the criteria of constituent (B). Particular preference is given to the use of low molecular weight SiH-functional compounds such as tetrakis(dimethylsiloxy)silane and tetramethylcyclotetrasiloxane, and also of SiH-containing siloxanes of higher molecular weight, such as poly(hydro-methyl)siloxane and poly(dimethylhydromethyl)siloxane, or analogous SiH-containing compounds in which some of the methyl groups have been replaced by 3,3,3-trifluoropropyl or phenyl groups.
Particularly preferred, as constituent (B), is the use of SiH-containing, essentially linear poly(hydromethyl)siloxanes and poly(dimethylhydromethyl)siloxanes, which may also be hydrodimethylsiloxy-terminated, having a viscosity in the range from 1 to 100 000 mPa·s, preferably in the range of 2 to 1000 mPa·s, more preferably in the range of 3 to 750 mPa·s, especially preferably in the range of 5 to 500 mPa·s, in each case at 25° C., and the use of hydrodimethylsiloxy-terminated polydimethylsiloxanes having a viscosity of 10 to 100 000 mPa·s, more preferably of 15 to 20 000 mPa·s, especially preferably 20 to 2000 mPa·s, in each case at 25° C., and mixtures thereof.
Constituent (B) is preferably present in the crosslinkable silicone compositions (S) of the invention in such an amount that the molar ratio of SiH groups to aliphatically unsaturated groups from (A) is 0.1 to 10, more preferably between 0.5 and 5.0, especially between 0.5 and 3.
Components (A) and (B) used in accordance with the invention are commercial products or preparable by standard chemical processes.
Rather than components (A) and (B), the silicone compositions (S) of the invention may contain organopolysiloxanes (C) simultaneously containing aliphatic carbon-carbon multiple bonds and Si-bonded hydrogen atoms. It is also possible for the silicone compositions (S) of the invention to contain all three components (A), (B) and (C).
If siloxanes (C) are used, these are preferably those composed of units of general formulae (IV), (V) and (VI)
R4fSiO4/2 (IV)
R4gR5SiO3-g/2 (V)
R4hHSiO3-h/2 (VI)
Examples of organopolysiloxanes (C) are those composed of SO4/2, R43SiO1/2, R42R5SiO1/2 and R42HSiO1/2 units, called MP resins, where these resins may additionally contain R4SiO3/2 and R42SiO units, and linear organopolysiloxanes consisting essentially of R42R5SiO1/2, R42SiO and R4HSiO units with R4 and R5 as defined above.
The organopolysiloxanes (C) preferably have an average viscosity of 0.01 to 500 000 Pa·s, more preferably 0.1 to 100 000 Pa·s, in each case at 25° C. Organopolysiloxanes (C) are preparable by standard chemical methods.
As hydrosilylation catalyst (D), it is possible to use any of the heat- or UV-curing catalysts known from the prior art. Component (D) may be a platinum group metal, for example platinum, rhodium, ruthenium, palladium, osmium or iridium, an organometallic compound or a combination thereof. Examples of component (D) are compounds such as hexachloroplatinum(IV) acid, platinum dichloride, platinum acetylacetonate and complexes of said compounds encapsulated in a matrix or a core/shell-type structure. The platinum complexes having low molecular weight of the organopolysiloxanes include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes with platinum. Further examples are platinum-phosphite complexes or platinum-phosphine complexes. For light- or UV-curing compositions, it is possible, for example, to use alkyl-platinum complexes such as derivatives of cyclopentadienyltrimethylplatinum(IV), cyclooctadienyldimethylplatinum(II) or diketonato complexes, for example bisacetylacetonatoplatinum(II), in order to initiate the addition reaction with the aid of light. These compounds may be encapsulated in a resin matrix.
The concentration of component (D) is sufficient for catalyzing the hydrosilylation reaction of components (A) and (B) and (C) on contact, in order to produce the heat required here in the process described. The amount of component (D) may be between 0.1 and 1000 parts per million (ppm), 0.5 and 100 ppm or 1 and 25 ppm of the platinum group metal, according to the total weight of the components. The curing rate may be low when the constituent of the platinum group metal is below 1 ppm. The use of more than 100 ppm of the platinum group metal is uneconomic or lowers the storage stability of the silicone composition.
The addition-crosslinking silicone compositions (S) may optionally contain all further additives that have also been used to date for production of addition-crosslinkable compositions. Examples of actively reinforcing fillers (E) not covered by the definition of the thermally conductive fillers (Z) that may be used as a component in the addition-crosslinking silicone compositions (Y) of the invention are fumed or precipitated silicas having BET surface areas of at least 50 m2/g, and carbon blacks and activated carbons such as furnace black and acetylene black, preference being given to fumed and precipitated silicas having BET surface areas of at least 50 m2/g.
The silica fillers (E) mentioned may have hydrophilic character or have been hydrophobized by known methods. Preferred fillers (E), as a result of the surface treatment, have a carbon content of at least 0.01% to a maximum of 20% by weight, preferably between 0.1% and 10% by weight, more preferably between 0.5% and 6% by weight.
In the addition-crosslinking silicone composition (S) of the invention, constituent (E) is preferably used in the form of a single finely divided filler or likewise preferably as a mixture of several thereof. The content of actively reinforcing filler in the crosslinkable silicone compositions (S) of the invention is in the range from 0% to 50% by weight, preferably 0% to 30% by weight, more preferably 0% to 10% by weight.
The crosslinkable addition-crosslinking silicone compositions (S) are more preferably characterized in that the filler (E) has been surface-treated. The surface treatment is achieved by the methods known in the prior art for hydrophobization of finely divided fillers C.
The addition-crosslinking silicone composition (S) of the invention may contain alkyltrialkoxysilanes (F) as further additions in order to reduce the viscosity thereof. If they are present, they are preferably present to an extent of 0.1-8% by weight, preferably 0.2-6% by weight, based on the total mass of silicone composition (S), where the alkyl group may be a saturated or unsaturated, linear or branched alkyl group having 2 to 20, preferably 8-18, carbon atoms, and the alkoxy groups may have 1 to 5 carbon atoms. Examples of the alkoxy groups include methoxy groups, ethoxy groups, propoxy groups and butoxy groups, particular preference being given to methoxy groups and ethoxy groups. Preferred for (F) is n-octyltri-methoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxy-silane, n-hexadecyltrimethoxysilane and n-octadecyltrimethoxy-silane.
The addition-crosslinking silicone composition (S) of the invention may optionally contain, as constituents, further additions in a proportion of up to 70% by weight, preferably up to 42% by weight, based in each case on the addition-crosslinking silicone composition (S) of the invention, these being different from the thermally conductive fillers (Z) of the invention and the additions (E) and (F). These additions may, for example, be inactive fillers, resinous polyorganosiloxanes other than the siloxanes (A), (B) and (C), non-reinforcing fillers, fungicides, fragrances, rheological additives, corrosion inhibitors, oxidation inhibitors, light stabilizers, retardants and compositions for influencing electrical properties, dispersing aids, adhesion promoters, pigments, dyes, plasticizers, organic polymers, heat stabilizers etc.
The crosslinkable heat-conducting silicone composition (Y) of the invention contains at least one thermally conductive filler (Z) having a thermal conductivity of at least 5 W/mK, with the proviso that the crosslinkable heat-conducting silicone compositions (Y) contain at least 20% by volume of metallic aluminum particles as thermally conductive fillers (Z) that still have to fulfill at least the further specific features a) to c), and the total amount of thermally conductive fillers (Z) is at least 50% by volume.
It is immaterial here whether a single fraction of aluminum particles (Z) having a SPAN within the range of the invention is used, or whether two or more fractions of aluminum particles are mixed and hence the inventive particle size distribution range according to feature c) of the inventive aluminum particles (Z) is achieved. If two or more fractions of aluminum particles are mixed, this may precede the mixing with one or more components of the composition of the invention, or the fractions of aluminum particles may also be mixed separately from one another with one or more components of the composition of the invention. The sequence of addition here does not matter.
Preferably not more than four fractions of aluminum particles are mixed so as to achieve the distribution range of the invention, preferably not more than three fractions of aluminum particles are mixed so as to achieve the distribution range of the invention, more preferably not more than two fractions of aluminum particles of the invention are used so as to achieve the distribution range of the invention, and especially preferably just a single aluminum powder of the invention is used.
Metallic aluminum has multiple very advantageous properties for use as a thermally conductive filler (Z). For example, the exceptionally high thermal conductivity of aluminum particles (Z) improves the thermal conductivity of the thermally conductive silicone composition (Y) produced therefrom. The low density of the aluminum particles (Z) reduces the weight of the composition and of the components produced therefrom and helps to save costs. The electrical conductivity can, if required by the application, be reduced by the prior art processes, for example by oxidation of the surface. The low Mohs hardness of the aluminum particles (Z) reduces abrasion in the course of processing. It will be clear to the person skilled in the art that the advantages mentioned are wholly or partly lost with decreasing purity of the aluminum. The purity of the aluminum particles (Z) of the invention and hence the aluminum content is at least is at least 80%, preferably at least 90%, more preferably at least 95%.
It is also known to the person skilled in the art that metallic aluminum particles are combustible under particular conditions and the dusts present an explosion risk. The person skilled in the art is also aware that the risk of dust formation, combustibility and explosion risk associated with metal powders increases significantly with decreasing particle size. For that reason, very small aluminum particles below 20 μm are unsuitable for many applications, for example as filler for gap fillers in lithium ion batteries. Such particles, on account of the low minimum ignition energy, are hazardous to handle and require complex and costly safety precautions in industrial processing. It has also been found that compositions containing very small aluminum particles below 20 μm are comparatively highly combustible and do not meet the UL94 V-0 combustibility class for gap fillers in lithium ion batteries.
The aluminum particles (Z) of the invention contain preferably less than 20% by weight, more preferably less than 15% by weight, especially preferably less than 10% by weight, of a particle fraction having a diameter of not more than 20 mm, based in each case on the total amount of aluminum particles.
The aluminum particles (Z) of the invention contain preferably less than 15% by weight, more preferably less than 10% by weight, especially preferably less than 5% by weight, of a particle fraction having a diameter of not more than 10 mm, based in each case on the total amount of aluminum particles.
The inventive aluminum particles (Z) preferably contain not more than 1.5% by weight of aluminum particles smaller than 2 μm, more preferably not more than 1% by weight, especially preferably not more than 0.5% by weight, based in each case on the total amount of aluminum particles. Especially preferred aluminum particles are essentially free of particle fractions smaller than 2 μm.
In an especially preferred embodiment, there is no intentional addition of aluminum particles having an average diameter of not more than 20 mm, more preferably of not more than 10 mm, especially of aluminum particles no larger than 5 mm.
Larger aluminum particles having an average particle size exceeding 20 μm have a comparatively high minimum ignition energy and are therefore more safely and easily processible in industrial processes. Nevertheless, compositions containing noninventive ground, angular aluminum particles larger than 20 μm were found to be comparatively highly combustible and did not meet the UL94 V-0 combustibility class for gap fillers in lithium ion batteries.
Aluminum particles having an average particle size exceeding 150 μm are unsuitable for many applications of heat-conducting silicone composition since such large-grain aluminum particles frequently do not fit into the fine gaps that have to be filled with gap fillers, for example. Moreover, it is found that, very unexpectedly, even such large-grain aluminum particles show comparatively high combustibility.
It has been found that, completely surprisingly, the crosslinkable silicone compositions (Y) of the invention are thermally conductive and simultaneously of low combustibility when they contain metallic aluminum particles (Z) of the invention that simultaneously fulfill features a) to c), in the required minimum amounts.
The crosslinkable silicone composition (Y) of the invention contains at least 20% by volume of such metallic aluminum particles (Z), preferably at least 25% by volume, more preferably at least 30% by volume, especially preferably at least 35% by volume. If the silicone composition (Y) contains smaller amounts of metallic aluminum particles (Z), the desired advantageous effects of the metallic aluminum, for example the low density and high thermal conductivity, are no longer sufficiently provided.
The prior art includes various methods of producing fine metallic particles. The aluminum particles (Z) of the invention are preferably produced from a molten state, as a result of which they have a comparatively smooth surface and are essentially free of fractures, sharp edges and pointed corners. In this way, they differ from conventional ground particles that have been converted to the final form, for example, by means of crushing, grinding or milling. It is immaterial here whether the particles are comminuted cold in a first process step, for example by grinding, and then converted to a molten form by heating above the melting point, for example by heat treatment in a hot zone, for example by means of a plasma, or whether an aluminum melt is first produced and then comminuted, for example by atomizing. The aluminum particles of the invention are preferably converted to the solid form of the invention by spraying or atomizing of an aluminum melt, followed by cooling.
Suitable methods of producing the aluminum particles (Z) of the invention are known to the person skilled in the art and are described, for example, in chapter 2.2 in “Pulvermetallurgie: Technologien und Werkstoffe [Powder Metallurgy: Technologies and Materials], Schatt, Werner, Wieters, Klaus-Peter, Kieback, Bernd, pp. 5-48, ISBN 978-3-540-681112-0, E-Book: https://doi.org/10.1007/978-3-540-68112-0_2”. Preferred processes for producing aluminum particles (Z) of the invention are inert gas atomization, also called gas atomization, pressurized water atomization, also called liquid atomization or water atomization methods, or melt spinning methods, also called centrifugal atomization or rotary atomization.
The processes described permit the production of metallic aluminum particles in a very different particle size range, especially in the average particle size range from a few micrometers to a few millimeters. It is also possible for the metallic aluminum particles to be produced in very different grain form, for example “spattered”, i.e. in very irregular, nodular, ellipsoidal or spherical form, and with a very variable range of particle size distribution. Irrespective of grain shape, these particles produced by means of a melting process have a comparatively smooth surface of the invention and are essentially free of fracture sites, sharp edges and pointed corners.
Completely surprisingly, it has been found that advantageous properties of the invention, especially comparatively low combustibility, are exhibited exclusively by those aluminum particles that are produced by a melting process, and hence show a predominantly rounded surface shape, and simultaneously fulfill the inventive features a) to c).
The production process for the metallic aluminum particles (Z) of the invention should preferably be executed in such a way that the particles are obtained in their predominantly rounded surface shape of the invention and hence fulfill features a)-c) and are essentially free of angular or sharp particles. The solidified particles may be separated by size in a subsequent process step by standard methods, for example by means of classifying by sieving or by means of sifting. In these methods, it is possible to separate agglomerates and bonded particles, but essentially no particles are destroyed.
What is meant by “rounded” and “essentially free of” is that the presence of such particles is tolerated within the scope of an impurity in the particles (Z) of the invention and does not disrupt their inventive effect.
The crosslinkable silicone composition (Y) of the invention may, as well as these metallic aluminum particles (Z), contain further thermally conductive fillers (Z) having thermal conductivity greater than 5 W/mK. Examples of such further thermally conductive fillers (Z) are magnesium oxide, metallic silicon powder, metallic silver powder, zinc oxide, boron nitride, aluminum carbide, aluminum nitride, aluminum hydroxide, aluminum oxide, graphite, and so forth. Preferred further fillers are aluminum powder, magnesium oxide, aluminum hydroxide, zinc oxide and aluminum oxide. Particularly preferred fillers are zinc oxides, metallic silicon powder, aluminum hydroxide and aluminum oxide, with metallic silicon powder and aluminum hydroxide being especially preferred. The shape of the further filler is fundamentally unrestricted. The particles may, for example, be of spherical, ellipsoidal, acicular, tubular, platelet, fibrous or irregular shape. They are preferably of spherical, ellipsoidal or irregular shape. The average diameter of the further thermally conductive fillers (Z) is preferably in the range of 0.01-150 μm, preferably in the range of 0.1-100 μm, more preferably in the range of 0.2-80 μm, especially in the range of 0.4-60 μm.
Fillers having very high density are disadvantageous in use in aircraft and electrical vehicles, for example, since they very significantly increase the weight of the components. The further thermally conductive fillers (Z) preferably have a density of not more than 6.0 kg/m3, preferably not more than 4.5 kg/m3, more preferably not more than 3.0 kg/m3.
The crosslinkable silicone composition (Y) of the invention preferably contains less than 16% by weight, preferably less than 14% by weight, more preferably less than 12% by weight, of a further heat-conducting filler (Z) having a density of greater than 5.0 kg/m3. In an especially preferred embodiment, the crosslinkable silicone composition (Y) of the invention is free of further heat-conducting fillers (Z) having a density of greater than 5.0 kg/m3.
The crosslinkable silicone composition (Y) of the invention preferably contains less than 35% by weight, preferably less than 30% by weight, more preferably less than 25% by weight, especially preferably less than 20% by weight, of a further heat-conducting filler (Z) having a density of greater than 3.0 kg/m3. In an especially preferred embodiment, the crosslinkable silicone composition (Y) of the invention is free of further heat-conducting fillers (Z) having a density of greater than 3.0 kg/m3.
Preferred crosslinkable silicone compositions (Y) of the invention contain, as thermally conductive filler (Z), metallic aluminum particles of the invention as the sole thermally conductive filler (Z) or in combination with up to two further thermally conductive fillers (Z). Impurities of up to 5% are not considered here to be a further filler (Z).
If the preferred compositions of the invention contain the metallic aluminum particles (Z) of the invention as the sole thermally conductive filler (Z) having a thermal conductivity greater than 5 W/mK, preference is given to adding a rheology modifier or thickener that prevents the settling of the filler. Suitable rheology modifiers are known to the person skilled in the art, preference being given to fumed silica, for example component (E).
The total amount of thermally conductive fillers (Z) in the crosslinkable heat-conducting silicone composition (Y) of the invention is 50-95% by volume, preferably 60-90% by volume, more preferably 65-88% by volume. If the silicone composition (Y) contains smaller amounts of heat-conducting filler (Z), thermal conductivity will be inadequate; if the silicone composition (Y) contains greater amounts of heat-conducting filler (Z), then the composition (Y) will be difficult to process since it will have high viscosity or even be brittle.
The uncrosslinked heat-conducting silicone compositions (Y) of the invention have a thermal conductivity of at least 0.6 W/mK, preferably at least 0.8 W/mK, more preferably at least 1.2 W/mK, especially at least 1.5 W/mK.
The viscosity of the uncrosslinked thermally conductive silicone compositions (Y) of the invention may vary within a very wide range and be matched to the requirements of the application. The viscosity of the uncrosslinked thermally conductive silicone compositions (Y) of the invention is preferably adjusted via the content of thermally conductive filler (Z) and/or the composition of the silicone composition (Z), by the standard methods from the art. These are known to the person skilled in the art. Preference is given to adjusting the viscosity via the selection and combination of components (A), (B) and (C) and optional addition of a rheology modifier and/or an active filler (E) and/or an alkyltrialkoxysilane (F).
The dynamic viscosity of the uncrosslinked, thermally conductive silicone compositions (Y) of the invention is preferably in the range of 100-1 000 000 mPa·s, preferably in the range of 1000-750 000 mPa·s, more preferably in the range of 2000-500 000 mPa·s, especially not more than 250 000 mPa·s, in each case at shear rate D=10 s−1 and 25° C.
The density of the uncrosslinked silicone compositions (Y) of the invention is less than 3.5 kg/m3, preferably less than 3.0 kg/m3, more preferably less than 2.6 kg/m3, especially less than 2.3 kg/m3.
The silicone compositions of the invention are predominantly free of volatile organic solvents, since these can form combustible vapors and/or lead to unwanted shrinkage during or after crosslinking. What is meant by “predominantly free” is that no solvents are added intentionally, and may instead only be present in small amounts of less than 0.1% by weight as an impurity in the inventive constituents of the silicone compositions of the invention.
The present invention further provides a process for producing the crosslinkable silicone compositions (Y) of the invention by mixing the individual components.
The components may be mixed by the customary continuous and batchwise prior art methods. Suitable mixing apparatus is any of the known apparatuses. Examples of these are uniaxial or biaxial continuous mixers, twin rollers, Ross mixers, Hobart mixers, dental mixers, planetary mixers, kneaders and Henschel mixers or similar mixers. Preference is given to mixing in a planetary mixer, a kneader or a continuous mixer. The crosslinkable silicone composition (Y) may optionally be heated in the course of mixing, preference being given to mixing within a temperature range of 15-40° C. The procedure for production of the preferred addition-crosslinkable silicone compositions (S) is also known to the person skilled in the art. In principle, the components may be added in any sequence. For example, components e) and optionally g) may be premixed and then mixed with components a) and/or b). It is optionally also possible here to heat and/or evacuate the mixture. Preference is given to mixing at least a portion of a) and the alkoxysilane g), then mixing in the heat-conducting filler(s) (Z). The production preferably takes place without active heating.
In a preferred embodiment, there is no intentional addition of aluminum particles having an average diameter of not less than 20 mm, more preferably of not less than 10 mm, especially of aluminum particles no larger than 5 mm, since this is associated with a particular safety risk in industrial production.
The crosslinkable silicone composition (Y) of the invention may be provided as a one-, two- or multicomponent mixture. Examples are two-component heat-curable compositions (Y) or one-component UV-crosslinkable compositions (Y). This has likewise long been known to the person skilled in the art.
The crosslinkable silicone composition (Y) of the invention has very good processing properties with regard to fluidity, gap-filling properties and layer thickness control, and can be applied precisely.
The temperature condition for the curing of the silicone composition (Y) which is preferably curable via hydrosilylation reaction is unlimited and is typically in the range from 20 to 180° C., preferably in the range from 20 to 150 C°, preferably in the range from 20 to 80 C°.
The present invention further provides the silicone products obtained by dispensing or applying and then crosslinking/curing the crosslinkable silicone composition. The cured silicone products (for example a heat-conducting element) show excellent thermal conductivity and exact layer thicknesses.
The hardness of the crosslinked thermally conductive silicone compositions (Y) of the invention may vary within a very wide range and be matched to the requirements of the application. For example, for the application as a gap filler, preference is given to using comparatively soft and flexible products, whereas, for example, for the application as a thermally conductive adhesive, preference is given to using comparatively hard and firm products. The hardness of the crosslinked thermally conductive silicone compositions (Y) of the invention is preferably adjusted via the composition of the silicone composition (S), by the standard methods from the prior art. These are known to the person skilled in the art. Preference is given to adjusting the hardness via the selection and combination of components (A), (B) and (C) and optional addition of a reinforcing filler (E).
The hardness of the cured silicone product is preferably in the range from 2 by the Shore 00 method to 100 by the Shore A method, preferably in the range from 10 by the Shore 00 method to 85 by the Shore A method. For the application as a gap filler, the hardness of the crosslinked thermally conductive silicone compositions of the invention is especially preferably in the range from 15 by the Shore 00 method to 65 by the Shore A method.
The crosslinked silicone products have a thermal conductivity of at least 0.6 W/mK, preferably at least 0.8 W/mK, more preferably at least 1.2 W/mK, especially at least 1.5 W/mK.
The present invention further provides for the use of the crosslinkable silicone composition as a gap filler (=heat-conducting element), heat-conducting pad, heat-conducting adhesives and encapsulating compounds. They are especially suitable for use as a gap filler for lithium ion batteries of electrical vehicles and as encapsulating compounds for electronic components, for example of electrical vehicles.
The density of the crosslinked silicone products of the invention is less than 3.5 kg/m3, preferably less than 3.0 kg/m3, more preferably less than 2.6 kg/m3, especially less than 2.3 kg/m3.
The crosslinked silicone products of the invention preferably conform to the UL94 V-0 combustibility class.
In a preferred embodiment, the density of the crosslinked silicone products of the invention is less than 2.5 kg/m3, and the thermal conductivity greater than 1.8 W/mK, and the combustibility satisfies UL94 V-0, with the proviso that the dynamic viscosity of the uncrosslinked silicone compositions of the invention is less than 500 000 mPa·s, especially less than 250 000, in each case at shear rate D=10 s−1 and 25° C.
In a particularly preferred embodiment, the density of the silicone products of the invention is less than 2.3 kg/m3, and the thermal conductivity greater than 1.8 W/mK, preferably greater than 3.0 W/mK, and the combustibility satisfies UL94 V-0, with the proviso that the dynamic viscosity of the uncrosslinked silicone compositions of the invention is less than 500 000 mPa·s, especially less than 250 000, in each case at shear rate D=10 s−1 and 25° C.
Thermal conductivity is determined to ASTM D5470-12 using a TIM Tester (Steinbeis Transferzentrum Wärmemanagement in der Elektronik, Lindenstr. 13/1, 72141 Walddorfhäslach, Germany). This determines the thermal resistance of the sample between 2 test cylinders by means of a constant heat flow. The layer thickness of the sample is used to calculate the effective thermal conductivity.
For the measurement, the sample is applied with the aid of a stencil and the measuring cylinder is narrowed manually to a thickness of 1.9-2.0 mm, then excess material is remove. Thermal conductivity is measured at a constant gap of 1.8-1.6-1.4-1.2-1.0 mm. Evaluation is effected by means of an integrated reporter position. After a plausibility test (straight-line coefficient of determination >0.998), the thermal conductivity lambda is reported as the effective thermal conductivity in W/(m*K).
Dynamic viscosity was measured using an Anton Paar MCR 302 rheometer according to DIN EN ISO 3219: 1994 and DIN 53019 by means of a flow curve with the following parameters: measurement type: T/D; temperature: 25.0° C.; measuring element: PP25; measurement gap: 0.50 mm; shear rate: 0.1-10 s−1; time: 120 sec; measurements: 30. The viscosity reported in Pa·s is an interpolated value at a shear rate of D=10 s−1.
The density of the uncrosslinked, thermally conductive silicone compositions was ascertained according to ISO 1183, and the density of the crosslinked thermally conductive silicone compositions according to ISO 1184.
Particle size (median diameter x50) and particle size distribution (parameter: distribution range SPAN) were analyzed with a Camsizer X2 from Retsch Technology (measurement principle: dynamic image analysis) according to ISO 13322-2 and ISO 9276-6 (method of analysis: dry measurement of powders and granules; measurement range: 0.8 μm-30 mm; compressed air dispersion with “X-Jet”; dispersion pressure=0.3 bar). Evaluations were volume-based and by the xc min model.
The examples which follow describe the basic implementability of the present invention, but without limiting it to the contents disclosed therein.
In the examples which follow, all figures for parts and percentages, unless stated otherwise, are based on weight. Unless stated otherwise, the examples which follow are conducted at a pressure of the surrounding atmosphere, i.e. at about 1000 hPa, and at room temperature, i.e. about 20° C. or a temperature which is established on combination of the reactants at room temperature without additional heating or cooling.
Table 1 summarizes the properties of the inventive and noninventive aluminum powders used in the examples.
Inventive examples 1-6 and 8 use inventive aluminum powder that have been obtained by means of inert gas atomization, and hence have a predominantly rounded surface shape, and additionally have a comparatively broad particle size distribution of the invention.
Noninventive comparative examples V1-V4 use noninventive aluminum powders that have been obtained by means of inert gas atomization, and hence are predominantly rounded, but have a comparatively narrow, noninventive particle size distribution and do not fulfill feature c) of the invention.
Noninventive comparative examples V5-V7 use noninventive aluminum powders that have a comparatively broad particle size distribution, but have been obtained by means of grinding methods, and hence are essentially angular and sharp-edged and do not fulfill feature b) of the invention.
Noninventive comparative examples V9 and V10 use noninventive aluminum powders that have been obtained by means of inert gas atomization, and hence are predominantly rounded, and additionally have a comparatively broad particle size distribution, but the particle size is comparatively small and does not fulfill feature a) of the invention.
100 g of the noninventive aluminum powder from comparative example V2, 200 g of the noninventive aluminum powder from comparative example V3, 400 g of a noninventive aluminum powder which has an x50 of 106.2 μm and a SPAN of 0.37 and has been produced by means of inert gas atomization and hence is essentially rounded, 200 g of a noninventive aluminum powder which has an x50 of 133.5 μm and a SPAN of 0.27 and has been produced by means of inert gas atomization and hence is essentially rounded, and 100 g of the noninventive aluminum powder from comparative example V4 are mixed homogeneously with a standard commercial RW 28 laboratory stirrer system (IKA®-Werke GmbH & CO. KG, 79219 Staufen, Germany). This gives an inventive aluminum powder mixture which has an x50 of 107.4 μm and a SPAN of 0.75 and is essentially rounded, and fulfills features a)-c) of the invention.
300 g of a noninventive aluminum powder which has an x50 of 133.5 μm and a SPAN of 0.27 and has been produced by means of inert gas atomization and hence is essentially rounded, and 600 g of the noninventive aluminum powder from comparative example V4 are mixed homogeneously with a standard commercial RW 28 laboratory stirrer system (IKA®-Werke GmbH & CO. KG, 79219 Staufen, Germany). This affords a noninventive aluminum powder mixture which has an x50 of 155.0 μm and a SPAN of 0.41, and does not fulfill feature a) of the invention.
24.5 g of a vinyldimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 1000 mPa·s, 16.3 g of a hydrodimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 1000 mPa·s, 1.0 g of a copolymer composed of dimethylsiloxy and methylhydrosiloxy and trimethylsiloxy units and having a viscosity of 200 mPa·s and a content of Si-bonded hydrogen of 0.18% by weight,
For the crosslinking, 4.18 g of ELASTOSIL® CAT PT (purchasable from Wacker Chemie AG, Hanns-Seidel-Platz 4, 81737 Munich, Germany) was added, corresponding to a mixing ratio of 1 part catalyst solution to 10 parts silicone composition, not counting the proportion of thermally conductive filler (Z). The mixture was mixed three times at 2350 rpm by SpeedMixer for 10 seconds, stirring the sample each time by spatula between the mixing operations. What is obtained is a reactive, pasty mass which is storable for only a few hours and was processed further directly.
A shaped body having dimensions of 207 mm×207 mm×2 mm was produced by means of compression vulcanization in a stainless steel mold at 165° C. and 380 N/cm2 for 5 minutes by the standard prior art methods. The vulcanizate was then subjected to heat treatment at 200° C. for 4 hours. What is obtained is a homogeneous and elastic shaped body.
Combustibility is tested in a simplified test based on UL 94 V, a standard from Underwriters Laboratories for testing of vertical burning that enables the classification of plastics by their flame retardancy. This method is the most common test for classification of flame-retardant plastics.
Test pieces each of length 5″ (127 mm) and width 0.5″ (12.7 mm) were punched out of the inventive shaped silicone bodies according to examples 9 to 16 and the noninventive shaped silicone bodies according to comparative examples V11 to V15 and V19 to V21. The plaque is secured in a vertical position at its upper end over a length of ¼″. 12″ (305 mm) beneath the test plaque is positioned a piece of cotton wool. The burner is adjusted such that a blue flame of length ¾″ is formed. The flame is directed from a distance of ⅜″ (9.5 mm) onto the lower edge of the plastic plaque. After contact for 10 seconds, the flame is removed. The afterflame time (total afterflame and afterglow time) for the test piece is noted. The sample should be extinguished immediately after the removal of the flame and burn for no more than a further 4 seconds. The test is conducted on 5 different test pieces, and the average value of the afterflame time is ascertained. The results can be found in table 2.
In noninventive comparative experiments V16 to V18, respectively containing 62.5% by volume of the noninventive aluminum particles according to comparative examples V5 to V7, which more particularly do not fulfill feature b), a silicone composition of very high viscosity was formed, which could not be pressed to give a suitable shaped silicone body.
In the testing of combustibility, it was found that comparative examples V11 to V15 and V19 to V23, containing a noninventive aluminum powder or a noninventive aluminum powder mixture according to comparative examples V1-V10 which does not fulfill one or more of features a) to c), show comparatively high combustibility. Especially noticeable was the combustibility of noninventive comparative sample V21, containing an aluminum powder having an average particle size of less than 20 μm. The sample continued to burn after the flame had been removed until the shaped body was completely burnt.
Entirely unexpectedly, it was found that aluminum powders that simultaneously fulfill features a)-c) show the inventive advantage of reduced combustibility. In inventive example 15, moreover, it was found, completely surprisingly, that mixing of multiple noninventive aluminum powders can produce an inventive aluminum powder mixture having the advantageous properties according to the invention of low combustibility, provided that the resultant mixture fulfills features a) to c). By contrast, the noninventive aluminum powder mixture from comparative example V8 does not fulfill features a) to c) and also does not show the advantages according to the invention.
The inventive shaped silicone bodies from inventive examples 12 and 13 and the noninventive shaped silicone bodies from noninventive comparative examples V11, V12 and V20 were subjected to the full combustibility test according to UL 94 V and classified as V-0, V-1 or V-2. For many industrial applications, especially for use as a gap filler in electrical vehicles, a V-0 classification is required. The results can be found in table 3.
According to general method GM1, an inventive crosslinkable thermally conductive silicone composition was produced by separately having, as aluminum powder, 191.0 g of the inventive aluminum powder from example 1 (37.6% by volume based on the total amount of the thermally conductive silicone composition) and 187.4 g of a noninventive aluminum powder which has an x50 of 106.2 mm and a SPAN of 0.37 and has been produced by means of inert gas atomization and hence is essentially rounded (36.8% by volume based on the total amount of the thermally conductive silicone composition) and mixing them in situ to form an inventive aluminum powder mixture.
What was obtained was an inventive reactive silicone composition having a content of inventive aluminum particles of 74.4% by volume and a dynamic viscosity of 58 600 mPa·s at shear rate D=10 s−1 and 25° C. The thermal conductivity was 4.65 W/mK and the density 2.19 kg/m3. The mass of the invention has good processibility, high thermal conductivity and low density, and is of very good suitability for use as a gap filler. General method GM1 was used to produce an inventive crosslinked shaped silicone body. The afterflame time according to example 17 was 2.1 seconds. Example 18 resulted in a UL94 V-0 classification.
A crosslinked shaped silicone body was produced according to inventive example 19, except using 19.0% by volume of the aluminum powder from example 1 and 18.6% by volume of a noninventive aluminum powder which has an x50 of 106.2 mm and a SPAN of 0.37 and has been produced by means of inert gas atomization and hence is essentially rounded.
The noninventive shaped silicone body has a noninventive total content of thermally conductive filler (Z) of 37.6% by volume and has a thermal conductivity of 0.45 W/mK. Example 18 resulted in a UL94 V-1 classification. The composition is unsuitable for use as a gap filler.
In a commercial Labotop planetary mixer (PC Laborsystem GmbH, Maispracherstrasse 6, 4312 Magden, Switzerland), equipped with two bar stirrers and a stripper, 115.4 g of a vinyldimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 120 mPa·s, and 1.1 g of WACKER® CATALYST EP (purchasable from Wacker Chemie AG, Hanns-Seidel-Platz 4, 81737 Munich, Germany) were mixed at room temperature and a stirrer speed of 300 rpm for 5 minutes. 308.5 g of BAK-5 spherical alumina (purchasable from Shanghai Bestry Performance Materials Co., Ltd. Room 209, Yunchuang Space, 325 Yunqiao Road, Pudong, Shanghai) was added and incorporated homogeneously at 300 rpm under slightly reduced pressure (950 mbar) for 10 minutes. Subsequently, a total of 670.7 g of an inventive aluminum powder that has an x50 of 79.5 mm and a SPAN of 1.62 and has been produced by means of inert gas atomization and hence is essentially rounded was added in two portions (first portion: 447.1 g, second portion: 223.6 g), and each addition was followed by mixing under slightly reduced pressure (950 mbar) at 300 rpm for 10 minutes. The resultant pasty mass was homogenized at 300 rpm under slightly reduced pressure (950 mbar) for a further 10 minutes. An inventive A component having a content of inventive aluminum particles of 55.5% by volume and a total content of thermally conductive filler of 73.1% by volume was obtained. The pasty composition has a density of 2.46 kg/m3, a dynamic viscosity of 57 800 mPa·s at shear rate D=10 s−1 and 25° C. and a thermal conductivity of 3.2 W/mK and is thus of very good suitability for use as a gap filler.
In a commercial Labotop planetary mixer (PC Laborsystem GmbH, Maispracherstrasse 6, 4312 Magden, Switzerland), equipped with two bar stirrers and a stripper, 106.5 g of a vinyldimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 120 mPa·s, and 9.0 g of a copolymer composed of dimethylsiloxy and methylhydrosiloxy and trimethylsiloxy units and having a viscosity of 200 mPa·s and a content of Si-bonded hydrogen of 0.18% by weight were mixed at room temperature and a stirrer speed of 300 rpm for 5 minutes. 306.0 g of BAK-5 spherical alumina (purchasable from Shanghai Bestry Performance Materials Co., Ltd. Room 209, Yunchuang Space, 325 Yunqiao Road, Pudong, Shanghai) was added and incorporated homogeneously at 300 rpm under slightly reduced pressure (950 mbar) for 10 minutes. Subsequently, a total of 665.2 g of an inventive aluminum powder that has an x50 of 79.5 mm and a SPAN of 1.62 and has been produced by means of inert gas atomization and hence is essentially rounded was added in two portions (first portion: 443.5 g, second portion: 221.7 g), and each addition was followed by mixing under slightly reduced pressure (950 mbar) at 300 rpm for 10 minutes. The resultant pasty mass was homogenized at 300 rpm under slightly reduced pressure (950 mbar) for a further 10 minutes. An inventive B component having a content of inventive aluminum particles of 55.5% by volume and a total content of thermally conductive filler of 73.1% by volume was obtained. The pasty composition has a density of 2.46 kg/m3, a dynamic viscosity of 42 800 mPa·s at shear rate D=10 s−1 and 25° C. and a thermal conductivity of 3.5 W/mK and is thus of very good suitability for use as a gap filler.
An inventive crosslinked specimen was produced by homogeneously mixing 1 part by weight of the inventive A component and 1 part by weight of the inventive B component, followed by vulcanization according to general method GM1. The resultant shaped body has a Shore A hardness of 1.6. Example 18 resulted in a UL94 V-0 classification. The composition is of very good suitability for use as a gap filler.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/052024 | 1/28/2022 | WO |
