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WO2025166729A1 - A polysiloxane composition - Google Patents

A polysiloxane composition

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Publication number
WO2025166729A1
WO2025166729A1 PCT/CN2024/076944 CN2024076944W WO2025166729A1 WO 2025166729 A1 WO2025166729 A1 WO 2025166729A1 CN 2024076944 W CN2024076944 W CN 2024076944W WO 2025166729 A1 WO2025166729 A1 WO 2025166729A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
group
equal
composition
titanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/076944
Other languages
French (fr)
Inventor
Junshan YIN
Haigang KANG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Priority to PCT/CN2024/076944 priority Critical patent/WO2025166729A1/en
Publication of WO2025166729A1 publication Critical patent/WO2025166729A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3684—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Definitions

  • Example 1 disclosed a thermally conductive composition containing silicone resin, alumina trihydrate (ATH) and isopropyl trioleyl titanate. That is, 16wt%silicone resin and 84wt%alumina trihydrate (ATH) were mixed. As the alumina trihydrate, those having a particle diameter of 5 ⁇ m and those having a particle diameter of 50 ⁇ m were mixed and added in a weight ratio of 40: 60. Then 0.5 parts by weight of isopropyl trioleyl titanate was added based on 100 parts by weight of the alumina trihydrate and uniformly mixed with a planetary mixer to obtain a thermally conductive composition for a heat dissipation pad.
  • silicone resin alumina trihydrate
  • ATH isopropyl trioleyl titanate
  • CN1264932C discloses a method for modifying mica filler with titanate.
  • the diluent acetone is used to prepare a titanate solution.
  • the titanate solution and the filler are mixed for 10-30 minutes under high-speed stirring, and the temperature is controlled to be less than or equal to 90°C.
  • CN106118136A discloses a method for treating calcium carbonate with titanate and stearic acid. Ex.3 discloses that the calcium carbonate was first treated with titanate for 8 minutes, and then the filler was treated with stearic acid for 15 minutes under 120 °C.
  • the present invention also desires to obtain a composition having simultaneously lower viscosity lower density and higher thermal conductivity at a high filling rate.
  • a treated filler (CE) obtained by mixing a component (C) thermally conductive filler with a component (E-1) and a component (E-2) ,
  • Component (E-1) is an alkoxysilane shown by the following formula (1) and/or an oligomer having a degree of polymerization of 2-5, R 1 a R 2 b Si (OR 3 ) 4-a-b (1)
  • each R 1 or R 2 or R 3 independently represents an alkyl group having 1 to 3 carbon atoms, preferably methyl, ethyl,
  • a represents an integer of 1 to 3
  • b represents an integer of 0 to 2, provided that a+b is an integer of 1 to 3;
  • Component (E-2) is a titanate represented by the following general formula (2) and/or an oligomer having a degree of polymerization of 2-5, (R 4 COO) m -Ti-OR 6 4-m (2)
  • R 4 is a hydrocarbon group containing 6-30 carbon atoms, and contains at least one carbon-carbon unsaturated group
  • n 1 or 2, preferably m is 2.
  • component (E-1) is one or more selected from the group consists of an alkoxysilane containing a C1-C3 short-chain alkyl group; preferably one or more selected from the group consists of a trialkoxysilane containing a C1-C3 short-chain alkyl group; more preferably one or more selected from the group consists of methyltrimethoxy silane, methyltriethoxy silane, ethyltrimethoxy silane, ethyltriethoxy silane.
  • component (E-1) is used in an amount between 0.05-0.15 wt%, preferably between 0.080-0.12 wt%, for example 0.07wt%, 0.09wt%, 0.11wt%, 0.13wt%, calculated on the basis that component (C) is 100 wt%.
  • Solvents selected from methanol, ethanol, isopropanol, butanol, acetone, ethyl acetate, formaldehyde, toluene, phthalates, mineral oil, vegetable oil, animal oil, decamethyl- cyclopentasiloxane, octamethyl cyclotetrasiloxane, polydimethylsiloxane with viscosity less than 5mPa. s.
  • the present invention provides a composition, which contains: a component (A) , that is an organopolysiloxane, preferably a component (A-1) that is an organopolysiloxane having two or more alkenyl groups per molecule;
  • component (B) that is an organohydrogenpolysiloxane having two or more hydrogen atoms directly bonded to silicon atoms and is contained in such an amount that the number of moles of hydrogen atoms directly bonded to silicon atoms in the component (B) is 0.1 to 5.0 times the number of moles of alkenyl groups derived from the component (A-1) ;
  • the filling rate total thermally conductive filler amount/total weight of the composition.
  • the filling rate which is greater than or equal to 0.88 is considered as the high filling rate.
  • the average particle diameter is 6, 8, 10, 12, 14, 16, 18 ⁇ m, and the content is 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, 32wt%, 34wt %, 36wt%,
  • the average particle diameter is 82, 84, 86, 88, 90, 92, 94, 96, 98 ⁇ m, and the content is 50wt%, 52wt%, 54wt%, 56wt%, 58wt%, 60wt%, 62wt%, 64wt%,
  • the component (C) in the composition is calculated as 100wt%.
  • composition as described above wherein the total amount of all aluminum hydroxide is greater than 95wt%, preferably greater than 99wt%, more preferably greater than 99.9wt%, and calculated based on the total amount of thermally conductive filler being 100wt%.
  • composition as described above wherein the total amount of all aluminum hydroxide is greater than 95wt%, preferably greater than 99wt%, and more preferably greater than 99.9wt%, and the total amount of fillers is calculated as 100wt%.
  • composition as described above wherein the density of the composition is equal to or less than 2.4 g/cm 3 , preferably equal to or less than 2.2 g/cm 3 , and more preferably equal to or less than 2.1 g/cm 3 .
  • composition as described above, wherein the thermal conductivity of the composition is greater than or equal to 3.1 W/mK, preferably greater than or equal to 3.2 W/mK.
  • (C-1) , (C-2) and (C-3) aluminum hydroxide is all in amorphous form.
  • the amount of the spherical filler is less than 10%by weight, preferably less than 1%by weight, calculated based on the weight of the composition as 100%by weight.
  • the amount of spherical alumina is less than 10%by weight, preferably less than 1%by weight, based on the weight of the composition as 100%by weight.
  • the content of Al (OH) 3 is greater than or equal to 99.1wt%, preferably greater than or equal to 99.5wt%.
  • composition as described above, wherein the ratio of (C-2) / (C-1) average particle diameter is between 8-12, preferably between 9-11, more preferably between 9.5-10.5, for example 9.6, 9.8, 10.0, 10.2, 10.4.
  • the particle size distribution of components in the component (C) is unimodal, or their particle sizes meet unimodal or almost unimodal particle size distributions.
  • the almost unimodal particle size distributions in the present invention means that in the volume integral map of the measurement sample, there might be two or more peaks, but the volume integral area of the main peak accounts for more than 80%of the entire volume integral area, preferably more than 85%, more preferably more than 90%, more preferably more than 95%.
  • Spherical fillers whose outer contour is generally spherical, are filler materials which are obtained from the amorphous fillers treated by chemical and/or physical (including heat treatment) processes.
  • Spherical alumina is a product obtained after heat treatment of amorphous alumina, and the outer contour is generally spherical.
  • thermoconductive silicone composition a silicone composition containing specific organopolysiloxane, hydrogenpolysiloxane, and thermally conductive filler is elaborately adjusted and formulated, so that the base material is filled with the thermally conductive filler at high density.
  • This makes it possible to provide a thermal conductive silicone composition having high thermal conductivity, low density, low viscosity and good storage stability: a thermal conductivity of 3.1 W/m ⁇ K or more and a density of 2.4 g/cm 3 or less.
  • thermal conductive silicone composition and its cured product is useful, particularly for cooling electronic parts through thermal conduction, as a heat conducting material interposed at an interface between a thermal surface of a heat-generating electronic part and a heat dissipating member such as a heat sink or a circuit substrate.
  • the present invention is a thermal conductive silicone composition
  • a thermal conductive silicone composition comprising:
  • Component (A) Organopolysiloxane, preferably Component (A-1) : Alkenyl Group-Containing Organopolysiloxane
  • Functional groups bonded to a silicon atom include an unsubstituted or substituted monovalent hydrocarbon group.
  • alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group; cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; aryl groups, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenylyl group
  • substituted groups include a chloromethyl group, a 2-bromoethyl group, a 3-chloropropyl group, a 3, 3, 3-trifluoropropyl group, a chlorophenyl group, a fluorophenyl group, a cyanoethyl group, a 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl group, etc.
  • Typical examples of the functional group include ones having 1 to 10 carbon atoms, and particularly typical examples thereof include ones having 1 to 6 carbon atoms.
  • the functional group include unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, a 3, 3, 3- trifluoropropyl group, and a cyanoethyl group; and unsubstituted or substituted phenyl groups, such as a phenyl group, a chlorophenyl group, and a fluorophenyl group. Additionally, all the functional groups bonded to a silicon atom do not have to be the same.
  • the alkenyl group normally has about 2 to 8 carbon atoms.
  • examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, etc.
  • lower alkenyl groups such as a vinyl group and an allyl group, are preferable and a vinyl group is particularly preferable.
  • the number of the alkenyl groups has to be two or more per molecule, and the alkenyl groups are each preferably bonded to only a silicon atom at a terminal of the molecular chain to make the resulting cured product have favorable flexibility.
  • the component (A-1) Alkenyl Group-Containing Organopolysiloxane has a viscosity at 25°C. in a range of preferably 10 to 100,000 mPa. s, particularly preferably 50 to 10,000 mPa. s, more preferably 50 to 1,000 mPa. s, more preferably 50 to 200 mPa. s.
  • the component (A-1) alkenyl group-Containing Organopolysiloxane is preferably a vinyl-terminated polydimethylsiloxane.
  • Optional Component (B) Organohydrogenpolysiloxane
  • Examples of the unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond as R′other than hydrogen in the formula (4) include alkyl groups, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group; cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; aryl groups, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl
  • the monovalent hydrocarbon group include unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, a 3, 3, 3-trifluoropropyl group, and a cyanoethyl group; and unsubstituted or substituted phenyl groups, such as a phenyl group, a chlorophenyl group, and a fluorophenyl group. Additionally, all R's do not have to be the same.
  • the amount of the Si-H groups derived from the component (B) is less than 0.1 moles relative to 1 mole of the alkenyl groups derived from the component (A-1) , no curing occurs, or the strength of the cured product is so insufficient that the molded product cannot keep the shape and cannot be handled in some cases. Meanwhile, if the amount exceeds 5.0 moles, the cured product may become inflexible and brittle.
  • component (B) could contains (B-1) and (B-2) .
  • the organic hydrogen-containing polysiloxane is an organic hydrogen-containing polysiloxane having at least 3, preferably 3-100 hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule, wherein the hydrogen content is between 0.5-4 mmol/g, preferably between 0.8-3 mmol/g, more preferably between 1.1-2.7 mmol/g, and more preferably between 1.5-2.3 mmol/g.
  • Component (B-2) the organic hydrogen-containing polysiloxane of component is an organic hydrogen-containing polysiloxane having 2 hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule, wherein hydrogen content is between 0.01-1.5 mmol/g, preferably between 0.1-1.2 mmol/g, more preferably between 0.3-1.0 mmol/g, more preferably between 0.4-0.8 mmol/g.
  • Component (C) Thermally conductive Filler
  • component (C) thermally conductive filler is a metal oxide and/or metal hydroxide.
  • the component (C) has to be blended in an amount of 800 to 4,000 parts by mass, preferably 900 to 2,000 parts by mass, more preferably 900 to 1, 500 parts by mass, relative to 100 parts by mass of the component (A) . If this blend amount is less than 800 parts by mass, the resulting composition has poor thermal conductivity. If the blend amount exceeds 2,000 parts by mass, the kneading operability is impaired, and the cured product becomes significantly brittle.
  • nH 2 O Na 2 PtCl 6 . nH 2 O, K 2 PtCl 4 . nH 2 O, PtCl 4 . nH 2 O, PtCl 2 , and Na 2 HPtCl 4 . nH 2 O
  • n is an integer of 0 to 6, preferably 0 or 6
  • alcohol-modified chloroplatinic acid see specification of U.S. Pat. No. 3,220,972
  • complexes of chloroplatinic acid with olefin see U.S. Pat. Nos.
  • Each R 5 independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • R 5 include alkyl groups, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group; cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; aryl groups, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a bi
  • the monovalent hydrocarbon group include unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, a 3, 3, 3-trifluoropropyl group, and a cyanoethyl group; and unsubstituted or substituted phenyl groups, such as a phenyl group, a chlorophenyl group, and a fluorophenyl group.
  • a methyl group and a phenyl group are particularly preferable.
  • d is preferably an integer of 5 to 2,000, particularly preferably an integer of 10 to 1,000, from the viewpoint of required viscosity.
  • Optional Component (G) Reaction Inhibitor
  • the inventive thermal conductive silicone composition may be further blended with other component (s) , as necessary.
  • the blendable optional components include heat resistance improvers, such as iron oxide and cerium oxide; viscosity adjusters, such as silica; colorants; release agents; etc.
  • the inventive product has a thermal conductivity of preferably 3.1 W/m ⁇ K or more, which is a measurement value measured at 25°C by transient hot wire method. Note that such a thermal conductivity can be adjusted by coordinating the type of the thermally conductive filler or combination of the particle diameter.
  • the inventive molded product is tested by a Zwick hardness tester. Note that such a hardness can be adjusted by changing the proportions of the component (A-1) and the component (B) to adjust the crosslinking density.
  • Component (A) is :
  • (A-1) an organopolysiloxane shown by the following formula (5) , wherein X represents a vinyl group, and n represents the number resulting in the viscosity of 120 mPa. s.
  • Treatment agent Ea di-isopropyl di-oleyl titanate, belongs to Component (E-2)
  • Treatment agent Eb isopropyl titanium triisostearate
  • Treatment agent Ec the mixture of 75wt%di-isopropyl di-oleyl titanate and 25wt%methyl-triethoxysilane
  • compositions were each poured into a mold with a size of 60 mm ⁇ 60 mm ⁇ 6 mm and were used to measure the thermal conductivity.
  • Density Density (Density) :
  • the measurement was performed by Mettler Toledo ML204.
  • thermoally conductive filler Component (C) in Table 1 is shown in Table 2.
  • Ex. 3 is a composition with good storage stability that meets the expectations of the present invention. Specifically, after 60 days of storage at room temperature, the viscosity is less than 180 Pa. s (or 180000 mPa. s) at 25°C according to DIN53019 at a shear rate of 10 (1/s) ., especially the viscosity change rate is less than 25%. Particularly, the viscosity change rate of Ex.3 is very low, less than 5%.
  • the thermal conductivity of Ex. 3 is greater than 3.1 W/mK and density of which is lower than 2.2 g/cm 3 .
  • C. Ex. 1, C. Ex. 2 and C. Ex. 4 have poor storage stability and a viscosity change rate greater than 25%, resulting in poor product performance in actual manufacture and use conditions.
  • C. Ex. 5 The composition has a higher initial viscosity and higher viscosity after storage.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a low viscosity silicone composition with high thermal conductivity. It contains vinyl silicone oil, thermally conductive and treatment agent. The composition can be used in the technical field of thermally conductive materials.

Description

A polysiloxane composition Technical field
The present invention relates to the technical field of thermally conductive silicone compositions.
Background
KR20210047752A Example 1 disclosed a thermally conductive composition containing silicone resin, alumina trihydrate (ATH) and isopropyl trioleyl titanate. That is, 16wt%silicone resin and 84wt%alumina trihydrate (ATH) were mixed. As the alumina trihydrate, those having a particle diameter of 5 μm and those having a particle diameter of 50 μm were mixed and added in a weight ratio of 40: 60. Then 0.5 parts by weight of isopropyl trioleyl titanate was added based on 100 parts by weight of the alumina trihydrate and uniformly mixed with a planetary mixer to obtain a thermally conductive composition for a heat dissipation pad.
KR102218858B1 Example 1 disclosed a thermally conductive gap filler containing oil, thermal conductivity filler, dispersant and antioxidant (mixed weight ratio: 8: 108: 1: 0.3) . The oil is synthetic polyalphaolefin oil. There dispersant is a mixture of an organic titanium compound (bis (oleato-O) bis (propan-2-olato) titanium) and oleic acid (mixed weight ratio: organic titanium compound: oleic acid = 40-50: 40-50) .
CN1264932C discloses a method for modifying mica filler with titanate. The diluent acetone is used to prepare a titanate solution. The titanate solution and the filler are mixed for 10-30 minutes under high-speed stirring, and the temperature is controlled to be less than or equal to 90℃.
CN106118136A discloses a method for treating calcium carbonate with titanate and stearic acid. Ex.3 discloses that the calcium carbonate was first treated with titanate for 8 minutes, and then the filler was treated with stearic acid for 15 minutes under 120 ℃.
Summary of Invention
The object of the present invention is to obtain a treated filler. Thermally conductive compositions with lower viscosity and good storage stability could be prepared by using this treated filler.
The present invention also desires to obtain a composition having simultaneously lower viscosity lower density and higher thermal conductivity at a high filling rate.
A treated filler (CE) obtained by mixing a component (C) thermally conductive filler with a component (E-1) and a component (E-2) ,
Component (E-1) is an alkoxysilane shown by the following formula (1) and/or an oligomer having a degree of polymerization of 2-5,
R1 aR2 bSi (OR3) 4-a-b     (1)
wherein each R1 or R2 or R3 independently represents an alkyl group having 1 to 3 carbon atoms, preferably methyl, ethyl,
a represents an integer of 1 to 3, and b represents an integer of 0 to 2, provided that a+b is an integer of 1 to 3;
Component (E-2) is a titanate represented by the following general formula (2) and/or an oligomer having a degree of polymerization of 2-5,
(R4COO) m-Ti-OR6 4-m    (2)
R4 is a hydrocarbon group containing 6-30 carbon atoms, and contains at least one carbon-carbon unsaturated group,
preferably, the number of carbon atoms is between 6-24, more preferably between 10-20, more preferably between 16-20; preferably contains 1-3 ethylenic bonds, preferably contains 1-2 ethylenic bonds, more preferably contains 1 ethylenic bond,
R4COO-is preferably an oleic acid group;
R6 is a hydrocarbon group containing 1-5 carbon atoms, preferably between 1-4 carbon atoms, more preferably methyl, ethyl, ethylene, allyl, propyl, isopropyl, butyl, isobutyl; more preferably propyl, isopropyl;
m is 1 or 2, preferably m is 2.
The treated filler (CE) as described above, wherein the mixing conditions are 90-160℃, greater than or equal to 2min; preferable greater than or equal to 6min; preferably 100-140℃, 6-70min; preferably 100-140℃, 8-50min; preferably 100-130℃, 8-45min; more preferably 115-125℃, 8-40min; more preferably 118-122℃, 8-35min; optional treatment temperature is 95℃, 98℃, 105℃, 110℃, 112℃, 116℃, 128℃, optional treatment time is 13min, 15min, 17min, 19min, 21min, 23min, 25min, 27min, 29 min, 31min, 34min, 38min, 40min, 42min, 45min, 50min, 52min, 55min.
The treated filler (CE) as described above, wherein component (E-1) a=1 and b=0.
The treated filler (CE) as described above, wherein component (E-1) is one or more selected from the group consists of an alkoxysilane containing a C1-C3 short-chain alkyl group; preferably one or more selected from the group consists of a trialkoxysilane containing a C1-C3 short-chain alkyl group; more preferably one or more selected from the group consists of methyltrimethoxy silane, methyltriethoxy silane, ethyltrimethoxy silane, ethyltriethoxy silane.
The treated filler (CE) as described above, wherein the sum of component (E-1) and component (E-2) is used in an amount between 0.05-2.00 wt%, preferably between 0.10-1.00 wt%, more preferably between 0.15-0.60 wt%, more preferably between 0.20-0.45 wt%, for example 0.23wt%, 0.28wt%, 0.33wt%, 0.35wt%, 0.38wt%, 0.40wt%, 0.42wt%, calculated on the basis that the amount of the thermally conductive filler in component (C) is 100 wt%.
The treated filler (CE) as described above, wherein component (E-1) is used in an amount between 0.05-0.15 wt%, preferably between 0.080-0.12 wt%, for example 0.07wt%, 0.09wt%, 0.11wt%, 0.13wt%, calculated on the basis that component (C) is 100 wt%.
The treated filler (CE) as described above, wherein component (E-2) is used in an amount between 0.15-0.45 wt%, preferably between 0.25-0.35wt%, for example 0.21wt%, 0.23wt%, 0.28wt%, 0.30wt%, 0.33wt%, 0.38wt%, calculated on the basis that the component (C) is 100 wt%.
The treated filler (CE) as described above, wherein the ratio of component (E-2) and component (E-1) is between 0.5-8, preferably between 0.8-5, more preferably between 1-4, for example 1.5, 2.0, 2.5, 2.8, 3.0, 3.2, 3.5, 3.8.
The treated filler (CE) as described above, wherein component (E-2) is one or more selected from the group consists of di-ethyl di-oleyl titanate, tri-ethyl oleyl titanate, di-n-propyl di-oleyl titanate, tri-n-propyl oleyl titanate, di-isopropyl di-oleyl titanate, tri-isopropyl oleyl titanate, di-butyl di-oleyl titanate, tri-butyl oleyl titanate, preferably one or more selected from the group consists of di-isopropyl di-oleyl titanate, tri-isopropyl oleyl titanate, more preferably di-isopropyl di-oleyl titanate.
A treating method for the component (C) thermally conductive filler, including mixing the component (C) with component (E-1) and component (E-2) , wherein the mixing conditions are 90-160℃, greater than or equal to 2min; preferable greater than or equal to 6min; preferably 100-140℃, 6-70min; preferably 100-140℃, 8-50min; preferably 100-130℃, 8-45min; more preferably 115-125℃, 8-40min; more preferably 118-122℃, 8-35min, optional treatment time is 13 min, 15 min, 17 min, 19 min, 21 min, 23 min, 25min, 27min, 29min, 31min, 34min, 36min, 38min, 40min, 45min, 50min, 55min.
According to the method mentioned above, under the condition of stirring, the component (C) thermally conductive filler is first subjected to nitrogen treatment, and then the component (E-1) and the component (E-2) is added.
According to the method mentioned above, the nitrogen inertization treatment time is greater than or equal to 5 minutes, preferably 5-60 minutes, more preferably 5-30 minutes, more preferably 5-15 minutes.
According to the method mentioned above, the temperature of nitrogen inertization treatment is room temperature.
According to the method mentioned above, component (E-1) and component (E-2) was applied by spraying and/or atomization.
The treated filler (CE) as described above, wherein the amount of solvent used in the mixing process is less than or equal to 1wt%, preferably less than or equal to 0.5wt%, more preferably less than or equal to 0.2wt%, more preferably less than or equal to 0.1wt%, calculated based on 100wt%of the thermally conductive filler component (C) .
Solvents selected from methanol, ethanol, isopropanol, butanol, acetone, ethyl acetate, formaldehyde, toluene, phthalates, mineral oil, vegetable oil, animal oil, decamethyl- cyclopentasiloxane, octamethyl cyclotetrasiloxane, polydimethylsiloxane with viscosity less than 5mPa. s.
The present invention provides a composition, which contains: a component (A) , that is an organopolysiloxane, preferably a component (A-1) that is an organopolysiloxane having two or more alkenyl groups per molecule;
optional a component (B) that is an organohydrogenpolysiloxane having two or more hydrogen atoms directly bonded to silicon atoms and is contained in such an amount that the number of moles of hydrogen atoms directly bonded to silicon atoms in the component (B) is 0.1 to 5.0 times the number of moles of alkenyl groups derived from the component (A-1) ;
the treated filler (CE) , wherein the filling rate of the treated filler (CE) is greater than or equal to 0.80, preferably greater than or equal to 0.84, preferably greater than or equal to 0.88, preferably greater than or equal to 0.89, preferably greater than or equal to 0.90;
optional a component (D) that is a platinum group metal-based curing catalyst having a platinum group metal element content of 0.1 to 1,000 ppm relative to the component (A-1) based on mass.
Use of the composition as described above in the field of caulking agent.
Use of the composition as described above in the field of potting.
In electronics, potting is a process of filling a complete electronic assembly with a solid or gelatinous compound for excluding gaseous phenomena, for resistance to shock and vibration, and for the exclusion of water, moisture, or corrosive agents.
For the above-mentioned composition, when the thermal conductivity is greater than 2.5 W/mk, preferably greater than 2.8 W/mk, more greater than 3.0 W/mk, at 25℃ according to DIN53019, when the shear rate is 10 (1/s) , the initial viscosity of the composition after mixing is less than 500 Pa. s, preferably less than 250 Pa. s, more preferably less than 200 Pa. s, more preferably less than 180 Pa. s.
For the above-mentioned composition, after stored in room temperature for 60 days, at 25℃ according to DIN53019, when the shear rate is 10 (1/s) , the viscosity of the composition is less than 300 Pa. s, preferably less than 250 Pa. s, more preferably less than 220 Pa. s, more preferably less than 200 Pa. s, more preferably less than 180 Pa. s.
For the above-mentioned composition, after stored in room temperature for 60 days, at 25℃ according to DIN53019, when the shear rate is 10 (1/s) , the viscosity change rate of the composition is less than 40%, preferably less than 30%, more preferably less than 25%, more preferably less than 15%, more preferably less than 10%, more preferably less than 5%.
the viscosity change rate= (initial viscosity-viscosity after stored in room temperature for 60 days) /initial viscosity
Compositions with lower viscosity change rates generally have good storage stability.
A thermally conductive member comprising the above composition or a cured product thereof. A heat dissipation structure including the above-mentioned thermally conductive member.
A heat dissipating structure comprising a heat dissipating component or a circuit board on which the heat dissipating component is mounted based on the above composition or a cured product thereof.
The above-mentioned heat dissipation structure is an electric/electronic device.
In the present invention, the filling rate = total thermally conductive filler amount/total weight of the composition. Generally, the filling rate which is greater than or equal to 0.88 is considered as the high filling rate.
In above mentioned composition or method, wherein the component (C) thermally conductive filler contains
10-25wt% (C-1) aluminum hydroxide with an average particle diameter greater than or equal to 0.1μm and less than or equal to 4μm,
for example (C-1) the average particle diameter is 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8 μm, and the content is 14wt%, 16wt%, 18wt%, 20wt%, 22wt%, 24wt%;
18-37wt% (C-2) aluminum hydroxide with an average particle diameter of 4μm or more and 20μm or less,
for example (C-2) the average particle diameter is 6, 8, 10, 12, 14, 16, 18μm, and the content is 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, 32wt%, 34wt %, 36wt%,
48-65wt% (C-3) aluminum hydroxide with an average particle diameter greater than or equal to 80μm and less than or equal to 100μm,
for example (C-3) the average particle diameter is 82, 84, 86, 88, 90, 92, 94, 96, 98 μm, and the content is 50wt%, 52wt%, 54wt%, 56wt%, 58wt%, 60wt%, 62wt%, 64wt%,
in (C-1) , (C-2) and (C-3) , the component (C) in the composition is calculated as 100wt%.
The composition as described above, wherein the total amount of all aluminum hydroxide is greater than 95wt%, preferably greater than 99wt%, more preferably greater than 99.9wt%, and calculated based on the total amount of thermally conductive filler being 100wt%.
The composition as described above, wherein the total amount of all aluminum hydroxide is greater than 95wt%, preferably greater than 99wt%, and more preferably greater than 99.9wt%, and the total amount of fillers is calculated as 100wt%.
The composition as described above, wherein the density of the composition is equal to or less than 2.4 g/cm3, preferably equal to or less than 2.2 g/cm3, and more preferably equal to or less than 2.1 g/cm3.
The composition as described above, wherein the thermal conductivity of the composition is greater than or equal to 3.1 W/mK, preferably greater than or equal to 3.2 W/mK.
In the composition as described above, (C-1) , (C-2) and (C-3) aluminum hydroxide is all in amorphous form.
In the composition as described above, the amount of the spherical filler is less than 10%by weight, preferably less than 1%by weight, calculated based on the weight of the composition as 100%by weight.
In the composition as described above, the amount of spherical alumina is less than 10%by weight, preferably less than 1%by weight, based on the weight of the composition as 100%by weight.
In the composition as described above, in (C-1) , (C-2) and (C-3) aluminum hydroxide, the content of Al (OH) 3 is greater than or equal to 99.1wt%, preferably greater than or equal to 99.5wt%.
The composition as described above, wherein (C-1) , (C-2) and (C-3) aluminum hydroxide, wherein the content of Na2O is less than or equal to 0.1wt%, preferably the total content of water-soluble Na2O and lattice state Na2O is less than or equal to 0.1wt%.
The composition as described above, wherein component (C) containing
15-25 wt% (C-1) Aluminum hydroxide with an average particle diameter greater than or equal to 0.5μm and less than or equal to 3μm,
18-25wt% (C-2) Aluminum hydroxide with an average particle diameter greater than or equal to 7μm and greater than or equal to 15μm,
50-65wt% (C-3) Aluminum hydroxide with an average particle diameter greater than or equal to 85μm and greater than or equal to 95μm,
in (C-1) , (C-2) and (C-3) , the component (C) is calculated as 100%by weight.
The composition as described above, wherein the surface-treated aluminum hydroxide is greater than 90wt%, preferably greater than 95wt%, more preferably greater than 99wt%, wherein the component (C) is calculated as 100wt%.
The composition as described above, wherein the weight ratio of (C-1) / (C-3) is between 0.2 and 0.4, preferably between 0.22 and 0.38, for example 0.25, 0.27, 0.29, 0.31, 0.33, 0.35.
The composition as described above, wherein the weight ratio of (C-2) / (C-3) is between 0.2 and 0.8, preferably between 0.25 and 0.75, for example 0.23, 0.28, 0.30, 0.31, 0.33, 0.35, 0.4, 0.5, 0.6, 0.7.
The composition as described above, wherein the weight ratio of (C-1) : (C-2) : (C-3) is preferably 1: (0.5-1.5) : (2.5-3.5) , more preferably 1: (0.8-1.2) : (2.8-3.2) .
The composition as described above, wherein the ratio of (C-2) / (C-1) average particle diameter is between 8-12, preferably between 9-11, more preferably between 9.5-10.5, for example 9.6, 9.8, 10.0, 10.2, 10.4.
The composition as described above, wherein the ratio of (C-3) / (C-1) average particle diameter is between 70-120, preferably between 75-100, more preferably between 80-99, for example 82, 84, 86, 88, 90, 92, 94, 96, 98.
The composition as described above, wherein the ratio of (C-3) / (C-2) average particle diameter is between 7.0-12.0, preferably between 7.5-10, more preferably between 8.0-9.9, for example 8.2, 8.4, 8.6, 8.8, 9.0, 9.2, 9.4, 9.6, 9.8.
Composition as described above, wherein component (C) contains
20-50wt% (C-5) alumina with an average particle diameter greater than or equal to 1 μm and less than or equal to 10 μm,
50-80wt% (C-6) alumina with an average particle diameter greater than or equal to 30 μm and less than or equal to 95 μm,
wherein the (C) component is calculated as 100wt%.
The definition of the average particle diameter refers to the value of the cumulative average particle diameter (D50 median diameter) measured by the particle size analyzer LS 13 320 manufactured by BECKMAN COULTER on a volume basis.
(C-1) the aluminum hydroxide sample is prepared by the solution method. 0.1g (C-1) sample is placed in 10ml of absolute ethanol, dispersed by ultrasonic (100w) and stirred for 2 minutes, so that the aluminum hydroxide is fully dispersed. Take out 2-3 drops of sample solution and put them into the sample cell of the particle size analyzer.
(C-2) and (C-3) aluminum hydroxide samples (or other thermally conductive fillers with an average particle diameter greater than or equal to 7μm) are prepared by the dry powder method, and an appropriate amount of the sample dried at room temperature is placed into the loading cylinder of the particle size analyzer. Insert the loading cylinder into the detection slot of the device.
In the present invention, the particle size distribution of components in the component (C) is unimodal, or their particle sizes meet unimodal or almost unimodal particle size distributions. The almost unimodal particle size distributions in the present invention means that in the volume integral map of the measurement sample, there might be two or more peaks, but the volume integral area of the main peak accounts for more than 80%of the entire volume integral area, preferably more than 85%, more preferably more than 90%, more preferably more than 95%.
Spherical fillers, whose outer contour is generally spherical, are filler materials which are obtained from the amorphous fillers treated by chemical and/or physical (including heat treatment) processes.
Spherical alumina is a product obtained after heat treatment of amorphous alumina, and the outer contour is generally spherical.
As described above, according to the inventive thermal conductive silicone composition, a silicone composition containing specific organopolysiloxane, hydrogenpolysiloxane, and  thermally conductive filler is elaborately adjusted and formulated, so that the base material is filled with the thermally conductive filler at high density. This makes it possible to provide a thermal conductive silicone composition having high thermal conductivity, low density, low viscosity and good storage stability: a thermal conductivity of 3.1 W/m·K or more and a density of 2.4 g/cm3 or less. Such a thermal conductive silicone composition and its cured product is useful, particularly for cooling electronic parts through thermal conduction, as a heat conducting material interposed at an interface between a thermal surface of a heat-generating electronic part and a heat dissipating member such as a heat sink or a circuit substrate.
Specifically, the present invention is a thermal conductive silicone composition comprising:
Component (A) : Organopolysiloxane, preferably Component (A-1) : Alkenyl Group-Containing Organopolysiloxane
The component (A) is an organopolysiloxane. The component (A) serves as a main component of the inventive composition. In general, the main chain portion is normally composed of repeated basic diorganosiloxane units, but this molecular structure may partially contain a branched structure, or a cyclic structure. Nevertheless, the main chain is preferably linear diorganopolysiloxane from the viewpoint of physical properties of the cured product, such as mechanical strength.
The component (A-1) is an alkenyl group-containing organopolysiloxane in which the number of silicon atom-bonded alkenyl groups is at least two per molecule. The component (A-1) serves as a main component of the inventive composition. In general, the main chain portion is normally composed of repeated basic diorganosiloxane units, but this molecular structure may partially contain a branched structure, or may be a cyclic structure. Nevertheless, the main chain is preferably linear diorganopolysiloxane from the viewpoint of physical properties of the cured product, such as mechanical strength.
Functional groups bonded to a silicon atom include an unsubstituted or substituted monovalent hydrocarbon group. Examples thereof include alkyl groups, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group; cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; aryl groups, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenylyl group; aralkyl groups, such as a benzyl group, a phenylethyl group, a phenylpropyl group, and a methylbenzyl group; and groups obtained from these groups by substituting a part or all of hydrogen atoms bonded to a carbon atom (s) therein with a cyano group, a halogen atom, such as fluorine, chlorine, and bromine, or the like. Examples of such substituted groups include a chloromethyl group, a 2-bromoethyl group, a 3-chloropropyl group, a 3, 3, 3-trifluoropropyl group, a chlorophenyl group, a fluorophenyl group, a cyanoethyl group, a 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl group, etc. Typical examples of the functional group include ones having 1 to 10 carbon atoms, and particularly typical examples thereof include ones having 1 to 6 carbon atoms. Preferable examples of the functional group include unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, a 3, 3, 3- trifluoropropyl group, and a cyanoethyl group; and unsubstituted or substituted phenyl groups, such as a phenyl group, a chlorophenyl group, and a fluorophenyl group. Additionally, all the functional groups bonded to a silicon atom do not have to be the same.
Furthermore, the alkenyl group normally has about 2 to 8 carbon atoms. Examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, etc. Among these, lower alkenyl groups, such as a vinyl group and an allyl group, are preferable and a vinyl group is particularly preferable. Note that the number of the alkenyl groups has to be two or more per molecule, and the alkenyl groups are each preferably bonded to only a silicon atom at a terminal of the molecular chain to make the resulting cured product have favorable flexibility.
The component (A) organopolysiloxane has a viscosity at 25℃. in a range of preferably 10 to 100,000 mPa. s, particularly preferably 50 to 50,000 mPa. s, more preferably 50 to 20,000 mPa. s, more preferably 50 to 2,000 mPa. s. The component (A) an organopolysiloxane is preferably a polydimethylsiloxane.
The component (A-1) : Alkenyl Group-Containing Organopolysiloxane has a viscosity at 25℃. in a range of preferably 10 to 100,000 mPa. s, particularly preferably 50 to 10,000 mPa. s, more preferably 50 to 1,000 mPa. s, more preferably 50 to 200 mPa. s. The component (A-1) alkenyl group-Containing Organopolysiloxane is preferably a vinyl-terminated polydimethylsiloxane.
One kind of the organopolysiloxane of the component (A) may be used alone, or two or more kinds thereof having different viscosity or the like may be used in combination.
One kind of the alkenyl group-containing organopolysiloxane of the component (A-1) may be used alone, or two or more kinds thereof having different viscosity or the like may be used in combination.
Optional Component (B) : Organohydrogenpolysiloxane
The component (B) is an organohydrogenpolysiloxane which has at least two, preferably 2 to 100, hydrogen atoms directly bonded to silicon atoms (Si-H groups) per molecule. This component works as a crosslinking agent of the component (A-1) . Specifically, a Si-H group in the component (B) is added to an alkenyl group in the component (A-1) by a hydrosilylation reaction that is promoted by a platinum group metal-based curing catalyst as the component (D) to be described later, thereby forming a three-dimensional network structure having a crosslinked structure. Note that if the number of Si-H groups per molecule in the component (B) is less than 2, no curing occurs.
The organohydrogenpolysiloxane to be used can be shown by the following average structural formula (4) but is not limited thereto.
In the formula, each R′independently represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and at least two R's are hydrogen atoms; e represents an integer of 1 or more.
Examples of the unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond as R′other than hydrogen in the formula (4) include alkyl groups, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group; cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; aryl groups, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenylyl group; aralkyl groups, such as a benzyl group, a phenylethyl group, a phenylpropyl group, and a methylbenzyl group; and groups obtained from these groups by substituting a part or all of hydrogen atoms bonded to a carbon atom (s) therein with a cyano group, a halogen atom, such as fluorine, chlorine, and bromine, or the like. Examples of such substituted groups include a chloromethyl group, a 2-bromoethyl group, a 3-chloropropyl group, a 3, 3, 3-trifluoropropyl group, a chlorophenyl group, a fluorophenyl group, a cyanoethyl group, a 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl group, etc. Typical examples of the monovalent hydrocarbon group include ones having 1 to 10 carbon atoms, and particularly typical examples thereof include ones having 1 to 6 carbon atoms. Preferable examples of the monovalent hydrocarbon group include unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, a 3, 3, 3-trifluoropropyl group, and a cyanoethyl group; and unsubstituted or substituted phenyl groups, such as a phenyl group, a chlorophenyl group, and a fluorophenyl group. Additionally, all R's do not have to be the same.
The amount of the component (B) added is such that, relative to 1 mole of alkenyl groups derived from the component (A-1) , the amount of Si-H groups derived from the component (B) is 0.1 to 5.0 moles (i.e., the number of moles of the hydrogen atoms directly bonded to silicon atoms is 0.1 to 5.0 times the number of moles of the alkenyl groups derived from the component (A-1) ) , preferably 0.3 to 2.0 moles, further preferably 0.5 to 1.0 moles. If the amount of the Si-H groups derived from the component (B) is less than 0.1 moles relative to 1 mole of the alkenyl groups derived from the component (A-1) , no curing occurs, or the strength of the cured product is so insufficient that the molded product cannot keep the shape and cannot be handled in some cases. Meanwhile, if the amount exceeds 5.0 moles, the cured product may become inflexible and brittle.
One kind of the organopolysiloxane of the component (B) may be used alone, or two or more kinds thereof having different viscosity or the like may be used in combination.
The composition as described above, wherein component (B) could contains (B-1) and (B-2) .
Component (B-1) the organic hydrogen-containing polysiloxane is an organic hydrogen-containing polysiloxane having at least 3, preferably 3-100 hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule, wherein the hydrogen content is between 0.5-4 mmol/g, preferably between 0.8-3 mmol/g, more preferably between 1.1-2.7 mmol/g, and more preferably between 1.5-2.3 mmol/g.
Component (B-2) the organic hydrogen-containing polysiloxane of component is an organic  hydrogen-containing polysiloxane having 2 hydrogen atoms (Si-H groups) directly bonded to silicon atoms in one molecule, wherein hydrogen content is between 0.01-1.5 mmol/g, preferably between 0.1-1.2 mmol/g, more preferably between 0.3-1.0 mmol/g, more preferably between 0.4-0.8 mmol/g.
The composition as described above, wherein component (B) contains (B-1) and (B-2) , and the amount of component (B-1) is between 0.5-3 wt%, preferably 1.5-2.5 wt%, based on the component (A-1) calculated as 100wt%.
The composition as described above, wherein component (B) contains (B-1) and (B-2) , and the amount of component (B-2) is between 10-50wt%, preferably between 20-40wt%, based on the component (A-1) calculated as 100wt%.
Component (C) : Thermally conductive Filler
Thermally conductive fillers generally do not contain fumed silica or precipitated silica.
In the composition of the present invention, the content of fumed silica and/or precipitated silica is less than 1 wt%preferably less than 0.1 wt%, calculated based on the total composition of 100 wt%.
The thermally conductive filler is not particularly limited. It is possible to use materials generally considered to be a thermally conductive filler, including non-magnetic metal, such as copper or aluminum; metal oxide, such as alumina, silica, magnesia, colcothar, beryllia, titania, or zirconia; metal nitride, such as aluminum nitride, silicon nitride, or boron nitride; metal hydroxide, such as aluminum hydroxide, magnesium hydroxide; artificial diamond, silicon carbide, etc. Additionally, the particle diameter of 0.1 to 200 μm may be employed. One or two or more kinds thereof may be used as a composite.
Preferably component (C) thermally conductive filler is a metal oxide and/or metal hydroxide. The component (C) has to be blended in an amount of 800 to 4,000 parts by mass, preferably 900 to 2,000 parts by mass, more preferably 900 to 1, 500 parts by mass, relative to 100 parts by mass of the component (A) . If this blend amount is less than 800 parts by mass, the resulting composition has poor thermal conductivity. If the blend amount exceeds 2,000 parts by mass, the kneading operability is impaired, and the cured product becomes significantly brittle.
Optional Component (D) : Platinum Group Metal-Based Curing Catalyst
The component (D) is a platinum group metal-based curing catalyst and is not particularly limited, as long as the catalyst promotes an addition reaction of an alkenyl group derived from the component (A-1) and a Si-H group derived from the component (B) . Examples of the catalyst include well-known catalysts used in hydrosilylation reaction. Specific examples include: platinum group metal simple substances, such as platinum (including platinum black) , rhodium, and palladium; platinum chloride, chloroplatinic acid, and chloroplatinate, such as H2PtCl4. nH2O, H2PtCl6. nH2O, NaHPtCl6. nH2O, KHPtCl6. nH2O, Na2PtCl6. nH2O, K2PtCl4. nH2O, PtCl4. nH2O, PtCl2, and Na2HPtCl4. nH2O (here, in the formulae, n is an integer  of 0 to 6, preferably 0 or 6) ; alcohol-modified chloroplatinic acid (see specification of U.S. Pat. No. 3,220,972) ; complexes of chloroplatinic acid with olefin (see U.S. Pat. Nos. 3,159,601 specification, 3,159,662 specification, and 3,775,452 specification) ; ones obtained by supporting a platinum group metal, such as platinum black and palladium, on a support, such as alumina, silica, or carbon; a rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst) ; complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with a vinyl group-containing siloxane, particularly a vinyl group-no more containing cyclic siloxane; etc.
The component (D) is used in such an amount that the platinum group metal element content is 0.1 to 1,000 ppm relative to the component (A-1) based on mass. If the content is less than 0.1 ppm, sufficient catalyst activity is not obtained. If the content exceeds 1,000 ppm, the cost is merely increased without enhancing the effect of promoting the addition reaction, and the catalyst remaining in the cured product may decrease the insulating property, too.
Component (F) : Property-Imparting Agent
As a component (F) , it is possible to add an organopolysiloxane having a viscosity at 25℃. of 10 to 100,000 mPa. s and shown by the following formula (3) ,
where each R5 independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms and no aliphatic unsaturated bond; and d represents an integer of 5 to 2,000.
The component (F) is used as appropriate in order to impart properties as a viscosity adjuster, plasticizer, and so forth for the thermal conductive silicone composition, but is not limited thereto. One kind of these may be alone, or two or more kinds thereof may be used in combination.
Each R5 independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of R5 include alkyl groups, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group; cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group; aryl groups, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenylyl group; aralkyl groups, such as a benzyl group, a phenylethyl group, a phenylpropyl group, and a methylbenzyl group; and groups obtained from these groups by substituting a part or all of hydrogen atoms bonded to a carbon atom (s) therein with a cyano group, a halogen atom, such as fluorine, chlorine, and bromine, or the like. Examples of such substituted groups include a chloromethyl group, a 2-bromoethyl group, a 3-chloropropyl group, a 3, 3, 3-trifluoropropyl group, a chlorophenyl group, a fluorophenyl group, a cyanoethyl group, a 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl group, etc. Typical examples of the monovalent hydrocarbon group include ones having 1 to 10 carbon atoms, and particularly typical examples thereof include ones having 1 to 6 carbon atoms. Preferable examples of the monovalent hydrocarbon group include unsubstituted or substituted  alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, a 3, 3, 3-trifluoropropyl group, and a cyanoethyl group; and unsubstituted or substituted phenyl groups, such as a phenyl group, a chlorophenyl group, and a fluorophenyl group. A methyl group and a phenyl group are particularly preferable. d is preferably an integer of 5 to 2,000, particularly preferably an integer of 10 to 1,000, from the viewpoint of required viscosity.
Moreover, the viscosity at 25℃. is preferably 10 to 100,000 mPa. s, particularly preferably 100 to 10,000 mPa. s. When the viscosity is 10 mPa. sor more, the cured product of the resulting composition hardly exhibits oil bleeding. When the viscosity is 100,000 mPa. s or less, the resulting thermal conductive silicone composition has suitable flexibility.
When the component (F) is added to the inventive thermal conductive silicone composition, the addition amount is not particularly limited, could be 10 to 100 parts by mass relative to 100 parts by mass of the component (A) . When the addition amount is in this range, this makes it easy to maintain the favorable flowability and operability of the thermal conductive silicone composition before curing, and to fill the composition with the component (C) thermally conductive filler.
In the inventive thermal conductive silicone composition, the dosage of the component (F) is preferably lower than 0.1 parts by mass, more preferably lower than 0.01 parts by mass, relative to 100 parts by mass of the component (A) . In this way, it is possible to avoid oil leakage and contamination of the substrate of the thermally conductive silicone composition.
Optional Component (G) : Reaction Inhibitor
As a component (G) , an addition reaction inhibitor is usable. As the addition reaction inhibitor, any of known addition reaction inhibitors used in usual addition reaction-curable silicone compositions can be employed. Examples thereof include acetylene compounds, such as 1-ethynyl-1-hexanol and 3-butyn-1-ol, various nitrogen compounds, organophosphorus compounds, oxime compounds, organochlorine compounds, etc. When the component (G) is blended, the use amount is preferably 0.01 to 1 parts by mass, more preferably 0.1 to 0.8 parts by mass, relative to 100 parts by mass of the component (A-1) . With such a blend amount, the curing reaction proceeds sufficiently, and the molding efficiency is not impaired.
Other Components
The inventive thermal conductive silicone composition may be further blended with other component (s) , as necessary. Examples of the blendable optional components include heat resistance improvers, such as iron oxide and cerium oxide; viscosity adjusters, such as silica; colorants; release agents; etc.
Embodiments
Thermal Conductive Silicone Cured Product, and Production Method Therefor
A thermal conductive silicone cured product (thermally conductive molded product) according to the present invention is a cured product of the above-described thermal conductive silicone composition. The curing conditions of curing (molding) the thermal conductive silicone composition may be the same as those for known addition reaction-curable silicone rubber compositions. For example, the thermal conductive silicone composition is sufficiently cured  at normal temperature, too, but may be heated as necessary. Preferably, the thermal conductive silicone composition is subjected to addition curing at 100 to 120℃ for 8 to 120 minutes. Such a cured product (molded product) of the present invention is excellent in thermal conduction.
Thermal conductivity of Molded Product
The inventive product has a thermal conductivity of preferably 3.1 W/m·K or more, which is a measurement value measured at 25℃ by transient hot wire method. Note that such a thermal conductivity can be adjusted by coordinating the type of the thermally conductive filler or combination of the particle diameter.
Hardness of Molded Product
The inventive molded product is tested by a Zwick hardness tester. Note that such a hardness can be adjusted by changing the proportions of the component (A-1) and the component (B) to adjust the crosslinking density.
According to DIN53019, an Anton Paar MCR302 instrument was used to test the kinematic viscosity and static viscosity of the composition of the present invention.
Components used in the following Examples and Comparative Examples are shown below.
Component (A) :
(A-1) an organopolysiloxane shown by the following formula (5) , wherein X represents a vinyl group, and n represents the number resulting in the viscosity of 120 mPa. s.
Component (C) :
(C-1) aluminum hydroxide with an average particle diameter of 1.5 μm
(C-2) aluminum hydroxide with an average particle diameter of 10 μm
(C-3) aluminum hydroxide with an average particle diameter of 90 μm
Component (D) :
a 2-ethyl hexanol solution of 5 wt%of chloroplatinic acid
Component (E-1) and Component (E-2) :
Treatment agent Ea, di-isopropyl di-oleyl titanate, belongs to Component (E-2)
Treatment agent Eb, isopropyl titanium triisostearate
Treatment agent Ec, the mixture of 75wt%di-isopropyl di-oleyl titanate and 25wt%methyl-triethoxysilane
Treatment agent Ed, the mixture of 75wt%isopropyl titanium triisostearate and 25wt%methyl-triethoxysilane
Treatment agent Ee, methyl-triethoxysilane, belongs to Component (E-1)
The above-mentioned materials are provided by Wacker Chemie AG or purchased on market.
Evaluation Methods Thermal conductivity:
The obtained compositions were each poured into a mold with a size of 60 mm×60 mm×6 mm and were used to measure the thermal conductivity.
Fill the paste sample into a 60mm×60mm×6mm mold and prepare at least 2 samples. Use a thermal conductivity meter (product name: TC3000E, manufactured by Xi'a n Xiatech Electronics Co., Ltd. ) , clamp the sensor of the tester in the middle of the sample, and test the thermal conductivity of the sample.
Density (Density) :
The measurement was performed by Mettler Toledo ML204.
Table 1 Silicone grease composition
The specific composition of "thermally conductive filler Component (C) " in Table 1 is shown in Table 2.
Table 2 thermally conductive filler Component (C)
In Table 1,
(a) place the thermally conductive filler (C) in the reaction kettle, and treat it with nitrogen for 10-15min under the condition of stirring at 25℃,
(b) heat the thermally conductive filler (C) to 120℃ within 5-10mins,
(c) mix the thermally conductive filler (C) with the treatment agent Ea, Eb, Ec, Ed, Ee at a weight ratio of 249: 1, and mix at 120℃ for 10min, 30min to obtain the premix of filler (C) and each treatment agent, that is the treated filler (CE) ,
(d) mix the premix with (A-1) to obtain the thermally conductive silicone grease compositions.
In the above steps, the speed of the high-speed mixer was 1400 RPM. This method belongs to the premix method.
Table 3 The viscosity changes of the Silicone grease composition after storage
Ex. 3 is a composition with good storage stability that meets the expectations of the present invention. Specifically, after 60 days of storage at room temperature, the viscosity is less than 180 Pa. s (or 180000 mPa. s) at 25℃ according to DIN53019 at a shear rate of 10 (1/s) ., especially the viscosity change rate is less than 25%. Particularly, the viscosity change rate of Ex.3 is very low, less than 5%. The thermal conductivity of Ex. 3 is greater than 3.1 W/mK and density of which is lower than 2.2 g/cm3.
C. Ex. 1, C. Ex. 2 and C. Ex. 4 have poor storage stability and a viscosity change rate greater than 25%, resulting in poor product performance in actual manufacture and use conditions. C. Ex. 5 The composition has a higher initial viscosity and higher viscosity after storage.

Claims (10)

  1. A treated filler (CE) obtained by mixing a component (C) thermally conductive filler with a component (E-1) and a component (E-2) ,
    Component (E-1) is an alkoxysilane shown by the following formula (1) and/or an oligomer having a degree of polymerization of 2-5,
    R1 aR2 bSi (OR3) 4-a-b   (1)
    wherein each R1 or R2 or R3 independently represents an alkyl group having 1 to 3 carbon atoms, preferably methyl, ethyl,
    a represents an integer of 1 to 3, and b represents an integer of 0 to 2, provided that a+b is an integer of 1 to 3;
    Component (E-2) is a titanate represented by the following general formula (2) and/or an oligomer having a degree of polymerization of 2-5,
    (R4COO) m-Ti-OR6 4-m       (2)
    R4 is a hydrocarbon group containing 6-30 carbon atoms, and contains at least one carbon-carbon unsaturated group,
    preferably, the number of carbon atoms is between 6-24, more preferably between 10-20, more preferably between 16-20; preferably contains 1-3 ethylenic bonds, preferably contains 1-2 ethylenic bonds, more preferably contains 1 ethylenic bond,
    R4COO-is preferably an oleic acid group;
    R6 is a hydrocarbon group containing 1-5 carbon atoms, preferably between 1-4 carbon atoms, more preferably methyl, ethyl, ethylene, allyl, propyl, isopropyl, butyl, isobutyl;
    more preferably propyl, isopropyl;
    m is 1 or 2, preferably m is 2.
  2. The treated filler (CE) as described in claim 1, wherein the mixing conditions are 90-160℃, greater than or equal to 2min; preferable greater than or equal to 6min; preferably 100-140℃, 6-70min; preferably 100-140℃, 8-50min; preferably 100-130℃, 8-45min; more preferably 115-125℃, 8-40min; more preferably 118-122℃, 8-35min.
  3. The treated filler (CE) as described in claim 1 or 2, wherein component (E-1) is one or more selected from the group consists of an alkoxysilane containing a C1-C3 short-chain alkyl group; preferably one or more selected from the group consists of a trialkoxysilane containing a C1-C3 short-chain alkyl group; more preferably one or more selected from the group consists of methyltrimethoxy silane, methyltriethoxy silane, ethyltrimethoxy silane, ethyltriethoxy silane.
  4. The treated filler (CE) as described in any of claim 1-3, wherein component (E-2) is one or more selected from the group consists of di-ethyl di-oleyl titanate, tri-ethyl oleyl titanate, di-n-propyl di-oleyl titanate, tri-n-propyl oleyl titanate, di-isopropyl di-oleyl titanate, tri-isopropyl oleyl titanate, di-butyl di-oleyl titanate, tri-butyl oleyl titanate, preferably one or more selected from the group consists of di-isopropyl di-oleyl titanate, tri-isopropyl oleyl titanate, more preferably di-isopropyl di-oleyl titanate.
  5. The treated filler (CE) as described in any of claim 1-4, wherein the ratio of component (E-2) and component (E-1) is between 0.5-8, preferably between 0.8-5, more preferably between 1-4.
  6. A treating method for the component (C) thermally conductive filler, including mixing the component (C) with component (E-1) and component (E-2) , wherein
    the mixing conditions are 90-160℃, greater than or equal to 2min; preferable greater than or equal to 6min; preferably 100-140℃, 6-70min; preferably 100-140℃, 8-50min;
    preferably 100-130℃, 8-45min; more preferably 115-125℃, 8-40min; more preferably 118-122℃, 8-35min.
  7. A composition, which contains:
    a component (A) , that is an organopolysiloxane, preferably a component (A-1) that is an organopolysiloxane having two or more alkenyl groups per molecule;
    optional a component (B) that is an organohydrogenpolysiloxane having two or more hydrogen atoms directly bonded to silicon atoms and is contained in such an amount that the number of moles of hydrogen atoms directly bonded to silicon atoms in the component (B) is 0.1 to 5.0 times the number of moles of alkenyl groups derived from the component (A-1) ;
    the treated filler (CE) in any of claim 1-5, wherein the filling rate of the treated filler (CE) is greater than or equal to 0.80, preferably greater than or equal to 0.84, preferably greater than or equal to 0.88, preferably greater than or equal to 0.89, preferably greater than or equal to 0.90;
    optional a component (D) that is a platinum group metal-based curing catalyst having a platinum group metal element content of 0.1 to 1,000 ppm relative to the component (A-1) based on mass.
  8. According to the filler in any of claim 1-5 or the method mentioned in claim 6 or the composition in claim 7, wherein the component (C) thermally conductive filler contains 10-25wt% (C-1) aluminum hydroxide with an average particle diameter greater than or equal to 0.1μm and less than or equal to 4μm,
    18-37wt% (C-2) aluminum hydroxide with an average particle diameter of 4μm or more and 20μm or less,
    48-65wt% (C-3) aluminum hydroxide with an average particle diameter greater than or equal to 80μm and less than or equal to 100μm,
    in (C-1) , (C-2) and (C-3) , the component (C) in the composition is calculated as 100wt%.
  9. A thermally conductive member comprising the composition in claim 7 or 8 or a cured product thereof.
  10. A heat dissipation structure including the thermally conductive member mentioned in claim 9.
PCT/CN2024/076944 2024-02-08 2024-02-08 A polysiloxane composition Pending WO2025166729A1 (en)

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