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WO2024185675A1 - Composition de résine de silicone thermoconductrice et élément thermoconducteur - Google Patents

Composition de résine de silicone thermoconductrice et élément thermoconducteur Download PDF

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Publication number
WO2024185675A1
WO2024185675A1 PCT/JP2024/007724 JP2024007724W WO2024185675A1 WO 2024185675 A1 WO2024185675 A1 WO 2024185675A1 JP 2024007724 W JP2024007724 W JP 2024007724W WO 2024185675 A1 WO2024185675 A1 WO 2024185675A1
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Prior art keywords
thermally conductive
silicone resin
resin composition
polyorganosiloxane
component
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Japanese (ja)
Inventor
智久 水野
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Taica Corp
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Taica Corp
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Priority to KR1020257021792A priority Critical patent/KR20250113506A/ko
Priority to JP2025505291A priority patent/JPWO2024185675A1/ja
Priority to CN202480009644.9A priority patent/CN120603902A/zh
Publication of WO2024185675A1 publication Critical patent/WO2024185675A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • 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
    • 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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • 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
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • 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
    • 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
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • 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

Definitions

  • the present invention relates primarily to a thermally conductive silicone resin composition used in a thermally conductive member for suppressing the temperature rise of a substrate being etched in a semiconductor etching apparatus. More specifically, the present invention relates to a thermally conductive silicone resin composition used in a thermally conductive member sandwiched between a focus ring and a mounting table that are installed on the outer periphery of a substrate being etched, and that provides stable adhesion to the substrate even in low temperature regions.
  • a substrate W to be processed such as a wafer is placed on a substrate placement unit 1 in a processing chamber, and a plasma of an etching gas or the like is irradiated to the substrate to be processed, thereby carrying out a predetermined etching process.
  • the substrate placement unit 1 is equipped with a placement table 2 (also called a lower electrode unit 2) equipped with a chuck mechanism 2a for placing and fixing the wafer W by an electrostatic chuck method or the like, and a support table 2b serving as a lower electrode, and a focus ring 3 (also called an edge ring) disposed on the outer periphery of the placement table 2.
  • the placement table 2 is cooled by a cooling unit 4 to adjust the temperature of the wafer W and the focus ring 3 to optimal conditions during the etching process. Note that there is also a configuration in which the focus ring 3 is placed on the placement table 2 via another accessory, but in this application, the structure in which the accessory is attached to the placement table is also generally referred to as the placement table 2.
  • the wafer W is placed on the lower electrode unit 2, which serves as a mounting table, and then while the inside of the processing chamber is maintained at a predetermined vacuum level, the wafer W is fixed with a chuck mechanism 2a, such as an electrostatic chuck, and a high-frequency voltage is applied between the lower electrode unit 2 and an upper electrode (not shown) installed opposite the lower electrode unit 2, generating a plasma of the etching gas in the processing chamber and etching the surface of the wafer W.
  • a chuck mechanism 2a such as an electrostatic chuck
  • the focus ring 3 functions to reduce discontinuity of the plasma in the area near the edge of the wafer W, so that the entire surface of the wafer W is uniformly plasma-processed.
  • the wafer W is cooled by adjusting the mounting table 2 to a low temperature.
  • Patent Document 1 discloses a mounting device for a workpiece in which a heat transfer medium is interposed between the mounting table and the focus ring, and a pressing means is provided to press and fix the focus ring to the mounting table.
  • Patent Document 2 also proposes a method in which a heat transfer sheet is placed between the focus ring and the mounting table, and the pressure in the chamber is restored to atmospheric pressure or a reduced pressure state after the chamber is suctioned to a vacuum prior to processing the substrate to be processed, thereby removing air from the gap between the heat transfer sheet and the mounting surface and bringing the heat transfer sheet into close contact with the mounting surface, thereby improving the thermal conduction of the focus ring.
  • Patent Document 3 proposes an etching method that includes a step of cooling the surface temperature of the substrate to -40°C or lower, a step of generating a plasma of a gas containing hydrogen and fluorine using high-frequency power for plasma generation, and a step of etching the laminated film with the generated plasma.
  • the thermally conductive member is used under conditions in which the temperature difference between the side that comes into contact with the focus ring, which is irradiated with plasma, and the side that comes into contact with the mounting table is significantly greater than before.
  • This causes stress to be generated in the thermally conductive member due to the difference in thermal expansion between the two sides, and if the surface of the thermally conductive member in contact with the mounting table hardens under the harsh low-temperature conditions, it becomes more likely to peel off from the mounting table, and its adhesion to the mounting table becomes weaker than before. If its adhesion to the mounting table decreases, the contact area between the mounting table and the thermally conductive member decreases, increasing thermal resistance, and thus increasing the risk of a malfunction that reduces the cooling performance of the focus ring.
  • Patent Document 4 discloses a gel cured product formed from a silicone composition containing an organopolysiloxane (A) containing a siloxane unit having a phenyl group and a vinyl group in the skeleton, a hydrogen polysiloxane (B) containing at least one hydrogen atom bonded to a silicon atom in each molecule, a platinum group metal catalyst (C), and aluminum oxide powder (D) that is a substantially spherical powder with an average particle size of 50 ⁇ m or less and has an alkali metal ion and halogen ion content of 5 ppm or less each when extracted for 20 hours under an atmosphere of 121°C, 2 atm, and 100% RH.
  • A organopolysiloxane
  • B hydrogen polysiloxane
  • C platinum group metal catalyst
  • D aluminum oxide powder
  • thermal conductive components are becoming more highly packed by increasing the proportion of thermally conductive filler.
  • the dispersibility of the thermally conductive filler in the resin matrix decreases, so a surface treatment agent that modifies the surface of the thermally conductive filler is added to improve the dispersibility of the thermally conductive filler and achieve high filling.
  • the amount of surface treatment agent added is set according to the amount of thermally conductive filler, so as the proportion of the thermally conductive filler increases due to high filling, the amount of surface treatment agent added increases, while the proportion of the silicone resin component, which is the resin matrix, decreases, and as a result, the ratio of the amount of surface treatment agent added to the amount of silicone resin component increases.
  • the present invention therefore aims to solve the above-mentioned problems of the prior art, and its purpose is to provide a thermally conductive silicone resin composition that can form a cured product that has both flexibility and high thermal conductivity under low temperature conditions, even when highly loaded with thermally conductive filler.
  • the second object of the present invention is to provide a heat conductive member or a heat conductive member for a semiconductor etching device that solves the above problems.
  • the thermally conductive silicone resin composition of the present invention is a thermally conductive silicone resin composition
  • a thermally conductive silicone resin composition comprising a silicone resin component containing polyorganosiloxane (A) having alkenyl groups at at least both ends, hydrogen polyorganosiloxane (B) having at least one hydrogen atom bonded to a silicon atom in one molecule, and a hydrosilylation catalyst (E), a thermally conductive filler (C), and a surface treatment agent (D) for surface treating the thermally conductive filler (C), in which component (A) is a phenyl-modified polyorganosiloxane having at least one phenyl group in the molecule, and component (B) is a phenyl-modified polyorganosiloxane having at least one phenyl group in the molecule.
  • the compounding ratio of component (C) is 300 to 2200 parts by weight per 100 parts by weight of the silicone resin component, and component (D) is a one-terminus hydrolyzable polyorganosiloxane in which a hydrolyzable group is bonded to a silicon atom at one terminus, and the compounding ratio of component (D) is 0.5 to 2 parts by weight per 100 parts by weight of component (C), and the cured product of this thermally conductive silicone resin composition has a low-temperature change rate of the complex elastic modulus of 1000% or less, calculated by dividing the absolute value of the difference between the complex elastic modulus at 20°C and -80°C by the complex elastic modulus at 20°C.
  • solidification refers to a state in which the thermal vibration of the molecular chains is reduced under low temperature conditions, the effect of intermolecular forces is increased, the molecular chains are aligned and crystallized, and the fluidity of a liquid is lost, or the flexibility of a cured product is lost.
  • the blending ratio of the thermally conductive filler (C) is 300 to 2200 parts by weight per 100 parts by weight of the silicone resin component, and as a surface treatment agent (D) for modifying the surface of the thermally conductive filler (C), 0.5 to 2 parts by weight of one-terminated hydrolyzable polyorganosiloxane is contained per 100 parts by weight of the thermally conductive filler (C).
  • the low-temperature change rate of the complex elastic modulus calculated by dividing the absolute value of the difference between the complex elastic modulus at 20°C and -80°C after curing, by the complex elastic modulus at 20°C, 1000% or less, flexibility is maintained even when the material is used under low-temperature conditions after curing, and adhesion to adherends such as cooling and heating elements is maintained, allowing the material to function stably as a heat conducting medium.
  • the hydrolyzable group in the one-terminated hydrolyzable polyorganosiloxane of component (D), which is the surface treatment agent is an alkoxy group. This more effectively suppresses solidification under low-temperature conditions, improving the effect of maintaining flexibility when the cured product is used under low-temperature conditions, and further improves the dispersibility of the thermally conductive filler (C) in the silicone resin component, achieving a uniform dispersion state and high loading.
  • the one-terminal hydrolyzable polyorganosiloxane of component (D) constituting the thermally conductive silicone resin composition of the present invention is a one-terminal trialkoxysilyl group-containing polyorganosiloxane. This allows a suitable compound to be selected as the surface treatment agent (D).
  • the one-terminated hydrolyzable polyorganosiloxane of component (D) constituting the thermally conductive silicone resin composition of the present invention has a phenyl group bonded to the polysiloxane chain.
  • the one-terminated hydrolyzable polyorganosiloxane of component (D) constituting the thermally conductive silicone resin composition of the present invention is a dimethylsiloxane-methylphenylsiloxane copolymer having a trimethoxysilyl group at one end.
  • the thermal conductivity of the cured product of the thermally conductive silicone resin composition of the present invention is 1.0 W/m ⁇ K or more. This allows for the production of a cured product that serves as a thermally conductive member with good thermal conductivity even under low temperature conditions.
  • the thermally conductive silicone resin composition of the present invention preferably has a hardness of 60 or less in Asker C hardness (based on JIS K6249) when cured. This allows for a cured product to be obtained that has good conformability and adhesion to the surface of the adherend even under low temperature conditions.
  • the heat-conducting member of the present invention is made of a cured product of the heat-conducting silicone resin composition described above. Because it combines flexibility and high thermal conductivity under low-temperature conditions, it has excellent adhesion to the adherend even in low-temperature environments and can function stably as a heat-conducting medium.
  • the thermally conductive member for a semiconductor etching apparatus of the present invention is made of a cured product of the above-mentioned thermally conductive silicone resin composition. Since it combines flexibility under low-temperature conditions with high thermal conductivity, even under etching conditions in which the plasma is highly powered in semiconductor etching processing, the thermally conductive member is less likely to increase in hardness (hardening) under plasma etching conditions, and by maintaining adhesion to the focus ring while maintaining adhesion to the mounting table, it is possible to stably suppress temperature rise in the focus ring. Since the temperature rise of the focus ring can be effectively suppressed, stable plasma etching processing can be achieved on an ongoing basis.
  • the thermally conductive silicone resin composition of the present invention comprises a silicone resin component that contains at least a polyorganosiloxane (A) having alkenyl groups at both ends, a hydrogen polyorganosiloxane (B) having at least one hydrogen atom bonded to a silicon atom in one molecule, and a hydrosilylation catalyst (E), and the components (A) and (B) are polyorganosiloxanes in which at least one phenyl group has been introduced in each molecule.
  • A polyorganosiloxane
  • B hydrogen polyorganosiloxane
  • E hydrosilylation catalyst
  • the silicone resin component, a thermally conductive filler (C), and the thermal The surface treatment agent (D) for treating the surface of the conductive filler (C) contains each component of a one-terminated hydrolyzable polyorganosiloxane, and each component is within a specific blending ratio, and the low-temperature change rate of the complex modulus obtained by dividing the absolute value of the difference between the complex modulus of the cured product at 20 ° C. and -80 ° C. by the complex modulus of 20 ° C. is 1000% or less. Therefore, even when the blending ratio of the thermally conductive filler is increased and a highly filled design is made, a cured product having both flexibility and high thermal conductivity under low-temperature conditions can be obtained.
  • the thermally conductive member made of the cured product of the thermally conductive silicone resin composition of the present invention has both flexibility and high thermal conductivity under low-temperature conditions, so that it can function as a stable thermally conductive medium with excellent adhesion to the adherend even in a low-temperature environment.
  • the thermally conductive member made of the cured product of the thermally conductive silicone resin composition of the present invention has both flexibility and high thermal conductivity under low-temperature conditions, so that it can function as a stable thermally conductive medium with excellent adhesion to the adherend even in a low-temperature environment.
  • semiconductor etching processing even if the focus ring is used in contact with the stage under low temperature conditions to cool the wafer during high-power plasma etching, adhesion to the stage and focus ring is ensured, and the temperature rise of the focus ring can be stably suppressed over time, allowing for uniform plasma etching of the entire wafer surface, while reducing the frequency of maintenance due to abnormal temperature rise in the focus ring,
  • 1 is a cross-sectional view showing an example of the structure of a plasma etching apparatus.
  • 1A to 1C are cross-sectional views showing an example of a structure in which a heat conductive member is arranged in a plasma etching apparatus and an embodiment of a heat conductive member for a semiconductor etching apparatus according to the present invention.
  • the thermally conductive silicone resin composition of the present invention is a thermally conductive silicone resin composition
  • a thermally conductive silicone resin composition comprising a silicone resin component containing a polyorganosiloxane (A) having alkenyl groups at at least both ends, a hydrogen polyorganosiloxane (B) having at least one hydrogen atom bonded to a silicon atom in one molecule, and a hydrosilylation catalyst (E), a thermally conductive filler (C), and a surface treatment agent (D) for surface treating the thermally conductive filler (C), in which the (A) component is a phenyl-modified polyorganosiloxane having at least one phenyl group in the molecule.
  • the (A) component is a phenyl-modified polyorganosiloxane having at least one phenyl group in the molecule.
  • the (B) component is a phenyl-modified hydrogen polyorganosiloxane having at least one phenyl group in the molecule, the blending ratio of the (C) component is 300 to 2200 parts by weight per 100 parts by weight of the silicone resin component, the (D) component is a one-terminus hydrolyzable polyorganosiloxane, and the blending ratio of the (D) component is 0.5 to 2 parts by weight per 100 parts by weight of the (C) component, and the low-temperature change rate of the complex elastic modulus of the cured product, calculated by dividing the absolute value of the difference between the complex elastic modulus at 20°C and -80°C by the complex elastic modulus at 20°C, is 1000% or less. This will be explained in detail below.
  • the silicone resin component that constitutes the thermally conductive silicone resin composition of the present invention contains a polyorganosiloxane (A) having alkenyl groups at both terminals, a hydrogen polyorganosiloxane (B) having at least one hydrogen atom bonded to a silicon atom in each molecule, and a hydrosilylation catalyst (E), and these components (A) and (B) undergo a crosslinking reaction to cure.
  • A polyorganosiloxane
  • B hydrogen polyorganosiloxane
  • E hydrosilylation catalyst
  • the polyorganosiloxane (A) constituting the silicone resin component is a polyorganosiloxane having alkenyl groups at least at both ends, and is a component that becomes the main skeleton of the silicone resin component that crosslinks with the hydrogen polyorganosiloxane (B) described later to form a cured product.
  • the polyorganosiloxane (A) is a phenyl-modified polyorganosiloxane having at least one phenyl group in the molecule, and it is considered that the steric hindrance action of the phenyl group in the molecule makes it difficult to solidify even under low temperature conditions and maintains flexibility.
  • the unreacted free oil is stably captured near the crosslinked gel structure by the stacking action of the phenyl group contained in the polyorganosiloxane (A), so that the bleeding of the unreacted free oil is suppressed.
  • the phenyl modification improves the radical resistance of the silicone resin component, the heat conductive member (cured product of the thermally conductive silicone resin composition) is less likely to be altered or deteriorated by plasma during plasma etching, and the plasma etching resistance can be improved.
  • An example of the phenyl-modified polyorganosiloxane is represented by the following general formula (1).
  • R1 is the same or different substituted or unsubstituted monovalent hydrocarbon group
  • R2 is a phenyl group
  • R3 and R4 are alkenyl groups
  • x and y are integers indicating the number of each unit, and each unit is arranged in blocks or randomly, preferably randomly.
  • R1 examples include alkyl groups such as methyl groups, ethyl groups, propyl groups, and butyl groups, cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, aryl groups such as phenyl groups and tolyl groups, aralkyl groups such as benzyl groups and phenylethyl groups, and halogenated hydrocarbons in which the hydrogen atoms of these groups are partially substituted with chlorine atoms, fluorine atoms, etc.
  • R3 and R4 include vinyl groups, allyl groups, butenyl groups, pentenyl groups, and hexenyl groups. From the viewpoint of material procurement, R3 and R4 are preferably vinyl groups.
  • the polyorganosiloxane (A) has a linear siloxane chain as shown in the above general formula (1), but the siloxane chain may have a branched structure. Additionally, as long as the effects of the present invention are not impaired, a portion of the siloxane chain may be replaced with a molecular chain such as a carbon chain.
  • the hydrogen polyorganosiloxane (B) constituting the silicone resin component has at least one hydrogen atom bonded to a silicon atom (hereinafter also referred to as SiH group) in one molecule, and acts as a crosslinking agent for curing the thermally conductive silicone resin composition by crosslinking with the alkenyl group of the polyorganosiloxane (A).
  • the hydrogen polyorganosiloxane (B) is a phenyl-modified hydrogen polyorganosiloxane having at least one phenyl group in the molecule, and has the same effect as the phenyl group of the polyorganosiloxane (A) due to the structure having a phenyl group in the molecule, so that it cooperates with the function of the phenyl group of the polyorganosiloxane (A) to contribute to further low-temperature flexibility and low oil bleeding properties.
  • the hydrogen polyorganosiloxane (B) is also phenyl-modified, so that the radical resistance of the silicone resin component is improved, so that the heat conductive member (cured product of the heat conductive silicone resin composition) is less likely to be altered or deteriorated by plasma during plasma etching, and the plasma etching resistance can be improved.
  • the phenyl-modified hydrogen polyorganosiloxane one represented by the following general formula (2) can be used.
  • R1 represents the same or different substituted or unsubstituted monovalent hydrocarbon group
  • R5, R6 and R7 represent R1, phenyl group or -H
  • at least two of R5, R6 and R7 are hydrogen atoms (-H) bonded to silicon atoms
  • s and t are integers indicating the number of each unit, and each unit is arranged in blocks or randomly, preferably randomly.
  • R1 examples include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group and phenylethyl group, or halogenated hydrocarbons in which the hydrogen atoms of these are partially substituted with chlorine atoms, fluorine atoms or the like.
  • the siloxane chain of the hydrogen polyorganosiloxane (B) is linear as in the above general formula (2), but the siloxane chain may be a branched structure. Additionally, as long as the effects of the present invention are not impaired, a portion of the siloxane chain may be replaced with a molecular chain such as a carbon chain.
  • the blending ratio of the polyorganosiloxane (A) and hydrogen polyorganosiloxane (B) constituting the silicone resin components of the thermally conductive silicone resin composition of the present invention is preferably set so that the hardness after the crosslinking reaction is 110 or less in terms of consistency (based on JIS K2220 1/4 cone). If the consistency exceeds 110, the curing may be insufficient or oil bleeding may be more likely to occur.
  • the number of hydrogen atoms bonded to silicon atoms of the hydrogen polyorganosiloxane (B) may be 0.5 to 2 as a ratio to the number of alkenyl groups of the polyorganosiloxane (A).
  • the polyorganosiloxane (A) and hydrogen polyorganosiloxane (B) constituting the silicone resin component may each be composed of a combination of multiple components. Also, a polysiloxane component that functions as a chain extender that reacts with the polymer main chain terminal of polyorganosiloxane (A) to link polyorganosiloxanes (A) together may be included.
  • polyorganosiloxane (A) and hydrogen polyorganosiloxane (B) are the main components of the silicone resin component according to the present invention, and from the viewpoint of fully exerting the effects of the present invention, the total amount of components (A) and (B) preferably accounts for 85% or more of the total amount of the silicone resin component, more preferably accounts for 90% or more, and particularly preferably accounts for 95% or more.
  • the hydrosilylation catalyst (E) constituting the silicone resin component is a component that promotes the crosslinking reaction by hydrosilylation reaction between the alkenyl group in the polyorganosiloxane (A) and the SiH group in the hydrogen polyorganosiloxane (B) described above, thereby facilitating the curing of the silicone resin component.
  • the hydrosilylation catalyst (E) is not particularly limited as long as it promotes the above-mentioned crosslinking reaction, and a known catalyst can be appropriately selected and applied, for example, a platinum-based, palladium-based, or rhodium-based catalyst.
  • platinum or a platinum compound which is relatively easy to obtain, is preferable, and more specifically, for example, a platinum simple substance, platinum black, chloroplatinic acid, a platinum-olefin complex, a platinum-alcohol complex, a platinum coordination compound, etc. can be mentioned.
  • the platinum-based catalyst may be used alone or in combination of two or more kinds.
  • the amount of hydrosilylation catalyst (E) to be blended is not particularly limited as long as it is a catalytic amount sufficient to promote the crosslinking reaction between polyorganosiloxane (A) and hydrogen polyorganosiloxane (B), but preferably, the amount is 0.1 to 500 ppm by mass, more preferably 1.0 to 100 ppm, calculated as the amount of metal atoms possessed by the hydrosilylation catalyst (E) relative to the weight of the silicone resin component. If the content of hydrosilylation catalyst (E) is less than 1.0 ppm, the catalytic effect may not be obtained, and if it exceeds 100 ppm, the catalytic effect will saturate, making it unprofitable in terms of raw material costs.
  • the thermally conductive filler (C) constituting the thermally conductive silicone resin composition of the present invention is a component that imparts thermal conductivity to the thermally conductive silicone resin composition, and can be a known thermally conductive filler.
  • Specific examples include those made of at least one material selected from the group consisting of metals, metal oxides, metal hydroxides, metal nitrides, metal carbides, and allotropes of carbon, and for example, in the case of use under plasma etching conditions, alumina, zinc oxide, magnesium oxide, aluminum nitride, boron nitride, and silicon carbide, which have good heat resistance, are more preferred.
  • the shape of the thermally conductive filler (C) may be any of spherical, irregular, and needle-like shapes, and is not particularly limited.
  • the thermally conductive filler (C) is preferably a combination of a large particle size filler and a small particle size filler from the viewpoint of improving the filling rate in the thermally conductive silicone resin composition while imparting appropriate fluidity to the thermally conductive silicone resin composition when uncured to improve moldability.
  • the large particle size filler has an average particle size of 10 to 120 ⁇ m, preferably 15 to 100 ⁇ m
  • the small particle size filler has an average particle size of 0.01 to 10 ⁇ m, preferably 0.1 to 4 ⁇ m.
  • the mixing ratio of the large particle size filler and the small particle size filler is appropriately set according to the filling rate of the thermally conductive filler (C) in the thermally conductive silicone resin composition and the design of the viscosity when uncured.
  • the average particle size of the thermally conductive filler (C) in the present invention can be determined as D 50 (median diameter) in particle size distribution measurement by laser light diffraction method.
  • the amount of thermally conductive filler (C) is 300 to 2200 parts by weight, and more preferably 500 to 2000 parts by weight, per 100 parts by weight of the silicone resin component, from the viewpoint of the good thermal conductivity and flexibility of the cured product required for the thermally conductive silicone resin composition. If the amount of thermally conductive filler (C) is less than 300 parts by weight, the thermally conductive silicone resin composition will not have sufficient thermal conductivity, and if it exceeds 2200 parts by weight, molding before curing will become difficult, and the flexibility of the cured product required for the thermally conductive silicone resin composition for semiconductor etching equipment will not be obtained.
  • the surface treatment agent (D) constituting the thermally conductive silicone resin composition of the present invention is a polyorganosiloxane in which a hydrolyzable group or a polar functional group is bonded to the silicon atom at one end of the molecular chain, and is a component for surface treating the thermally conductive filler (C).
  • the surface of the thermally conductive filler (C) is modified with the surface treatment agent (D), thereby improving the affinity between the thermally conductive filler (C) and the silicone resin component, improving the dispersibility of the thermally conductive filler (C) in the silicone resin component, and improving the adhesion of the interface between the thermally conductive filler (C) and the cured silicone resin component in the cured product of the thermally conductive silicone resin composition.
  • this surface treatment agent (D) suppresses the solidification of the thermally conductive filler (C) at the surface treatment interface in the thermally conductive silicone resin composition, and even when the composition is designed to have a high filling ratio of the thermally conductive filler, it plays an important role in maintaining the flexibility of the cured product of the thermally conductive silicone resin composition under low temperature conditions.
  • the surface treatment agent (D) is a one-terminus hydrolyzable polyorganosiloxane having a hydrolyzable group bonded to a silicon atom at one terminus.
  • the one-terminated hydrolyzable polyorganosiloxane of the surface treatment agent (D) is a polyorganosiloxane in which a hydrolyzable group (-OR8) is bonded to a silicon atom at one end of a molecular chain represented by the following general formula (3).
  • a hydrolyzable group (-OR8) is bonded to a silicon atom at one end of a molecular chain represented by the following general formula (3).
  • R1 independently represents a monovalent hydrocarbon group that is unsubstituted or substituted.
  • the monovalent hydrocarbon group of R1 is not particularly limited, but preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • Specific examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and halogenated hydrocarbon groups such as halogenated alkyl groups in which some or all of the hydrogen atoms of these monovalent hydrocarbon groups are substituted with halogen atoms such as chlorine, fluorine, and bromine.
  • the alkyl group may be linear, branched, or cyclic, and specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, n-hexyl, and n-octyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, and 2-ethylhexyl; and cyclic alkyl groups such as cyclopentyl and cyclohexyl.
  • alkenyl groups include vinyl, allyl, 1-butenyl, and 1-hexenyl groups.
  • aryl groups include phenyl and tolyl groups.
  • aralkyl groups include 2-phenylethyl and 2-methyl-2-phenylethyl groups.
  • halogenated alkyl groups include 3,3,3-trifluoropropyl, 2-(nonafluorobutyl)ethyl, and 2-(heptadecafluorooctyl)ethyl groups.
  • R1 in formula (3) is preferably a methyl group or a phenyl group.
  • n is preferably an integer from 2 to 100, more preferably an integer from 5 to 80, from the viewpoints of improving the workability and uniformity of the surface treatment of the thermally conductive filler (C) and its dispersibility in the silicone resin component, and of maintaining the flexibility of the cured product of the thermally conductive silicone resin composition under low temperature conditions. If n is less than 2, oil bleeding may occur more easily from the cured product. If n exceeds 100, the viscosity of the composition increases, which tends to reduce the workability of the surface treatment of the thermally conductive filler (C).
  • the R8s constituting the hydrolyzable group (-OR8) each independently represent an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group.
  • the alkyl group of R8 is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 6, and more preferably 1 to 3 carbon atoms, as in the groups exemplified for R1 above, and includes the same as in the specific examples.
  • the alkoxyalkyl group includes an alkoxy group and an alkyl group each having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, such as a methoxyethyl group and a methoxypropyl group.
  • the alkenyl group includes an alkenyl group having 2 to 6 carbon atoms, such as a vinyl group and an allyl group.
  • the acyl group includes an acyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as an acetyl group and an octanoyl group.
  • the hydrolyzable group (-OR8) is preferably an alkoxy group in which R8 is an alkyl group, more preferably a methoxy group or an ethoxy group in which R8 is a methyl group or an ethyl group, and particularly preferably a methoxy group.
  • a is an integer of 1 to 3.
  • polyorganosiloxanes having a polar functional group bonded to a silicon atom at one end are single-end functional polyorganosiloxanes having a polar functional group bonded to a silicon atom at one end of a molecular chain represented by the following general formula (4).
  • this polar functional group interacts with the surface of the thermally conductive filler (C) to improve the affinity between the thermally conductive filler (C) and the silicone resin component, improving the dispersibility of the thermally conductive filler (C) in the silicone resin component, as well as improving the adhesion at the interface between the thermally conductive filler (C) and the cured silicone resin component in the cured product of the thermally conductive silicone resin composition, and that the structure of the siloxane chain itself improves the flexibility of the cured product of the thermally conductive silicone resin composition under low temperature conditions.
  • R1 in formula (4) is the same as R1 in formula (3).
  • R9 in formula (4) is a polar functional group, and known groups can be used as long as the effects of the present invention are obtained.
  • n in formula (4) is preferably an integer of 2 to 100, more preferably an integer of 5 to 80, from the viewpoint of improving the workability and uniformity of the surface treatment of the thermally conductive filler (C) and the dispersibility in the silicone resin component, and from the viewpoint of maintaining the flexibility of the cured product of the thermally conductive silicone resin composition under low temperature conditions.
  • n is less than 2, oil bleeding may easily occur from the cured product. If n exceeds 100, the viscosity of the composition increases, and there is a tendency for the workability of the surface treatment of the thermally conductive filler (C) to decrease.
  • a in the formula is an integer of 1 to 3, and is preferably 3 from the viewpoint of the surface treatment effect of the thermally conductive filler (C).
  • the surface treatment agent (D) constituting the thermally conductive silicone resin composition of the present invention is preferably phenyl-modified by selecting a phenyl group as R1 of general formula (3) or general formula (4) bonded to the polysiloxane chain in any type of polyorganosiloxane represented by the above-mentioned general formula (3) or general formula (4).
  • This makes it possible to more effectively suppress solidification under low temperature conditions for the surface treatment layer formed on the surface of the thermally conductive filler (C), and further improves the dispersibility of the thermally conductive filler (C) in the silicone resin component, making it possible to highly pack the thermally conductive filler (C), thereby improving the thermal conductivity characteristics of the thermally conductive silicone resin composition.
  • the phenyl modification improves the radical resistance of the surface treatment agent (D), and thus, combined with the improvement in the radical resistance of the silicone resin component, the alteration and deterioration of the thermally conductive member (cured product of the thermally conductive silicone resin composition) due to plasma during plasma etching is further suppressed, and the plasma etching resistance can be further improved.
  • the surface treatment agent (D) is a one-terminated hydrolyzable polyorganosiloxane, it is more preferably a one-terminated trimethoxysilyl group dimethylsiloxane-methylphenylsiloxane copolymer.
  • the number and bonding positions of the phenyl groups bonded to the polysiloxane chain are appropriately set within a range in which the effects of the present invention can be obtained, but from the viewpoint of flexibility under low-temperature conditions, it is preferable that they are bonded to the silicon atom of the D unit.
  • the viscosity at 25°C of the polyorganosiloxane selected as the surface treatment agent (D) is preferably 0.005 to 10 Pa ⁇ s, more preferably 0.005 to 1 Pa ⁇ s. Within this range, oil bleeding from the cured product is suppressed, while the workability of the surface treatment of the thermally conductive filler (C) and its dispersibility in the silicone resin component are improved, allowing the affinity between the thermally conductive filler (C) and the silicone resin component to be more uniformly expressed.
  • the polyorganosiloxane selected as the surface treatment agent (D) has a glass transition temperature Tg of approximately -120°C. This provides the effect of suppressing the increase in hardness of the surface treatment layer formed near the surface of the thermally conductive filler (C) under low-temperature conditions, compared to alkyl-based silane coupling agents such as decyltrimethoxysilane.
  • the surface treatment agent (D) may be one of the following: one-terminal hydrolyzable polyorganosiloxane, one-terminal functional polyorganosiloxane, phenyl-modified one-terminal hydrolyzable polyorganosiloxane, and phenyl-modified one-terminal functional polyorganosiloxane. These may be used alone or in combination of two or more. Furthermore, conventional surface treatment agents such as silane coupling agents may be used in combination as long as the effects of the present invention are not impaired.
  • the siloxane chain is preferably linear, but the siloxane chain may have a branched structure.
  • a part of the siloxane chain may be replaced with a molecular chain such as a carbon chain, as long as the effect of the present invention is not impaired.
  • the blending ratio of the surface treatment agent (D) is 0.5 to 2 parts by weight, preferably 0.5 to 1.5 parts by weight, and more preferably 0.8 to 1.2 parts by weight, per 100 parts by weight of the total weight of the thermally conductive filler (C). If the blending ratio of the surface treatment agent (D) is less than 0.5 parts by weight, the affinity between the thermally conductive filler (C) and the silicone resin component is poor, and flexibility after curing may be lost, while if it exceeds 2 parts by weight, the thermal conductivity decreases and the material strength of the cured product of the thermally conductive resin composition may decrease.
  • the thermally conductive silicone resin composition of the present invention may contain other components, provided the components do not impair the objects and effects of the present invention.
  • additives for imparting functionality such as a heat stabilizer, a reaction inhibitor for adjusting the curing rate, a pigment or dye for coloring, a flame retardant, or a release agent for facilitating release from a mold or separator film.
  • the heat stabilizer is a component that can impart heat resistance and plasma etching resistance to the cured product of the thermally conductive silicone resin composition, as well as the effect of reducing the occurrence of oil bleeding.
  • heat stabilizers include carbon-based materials such as iron oxide, carbon black, graphite, carbon nanotubes, and carbon fibers, iron carboxylates, cesium hydrate, titania, barium zirconate, cerium octanoate, zirconium octanoate, and porphyrin, but it is preferable to use a heat stabilizer for a carbon-based material that does not act as an oxidizing agent under reduced pressure and heating conditions and has excellent radical trapping properties.
  • the heat stabilizer may be used alone or in combination.
  • the blending ratio of the heat stabilizer is 0.1 to 20 parts by weight, more preferably 5 to 15 parts by weight, and particularly preferably 5 to 10 parts by weight, per 100 parts by weight of the total of the polyorganosiloxane (A) and the hydrogen polyorganosiloxane (B). If the blending ratio of the heat stabilizer is less than 5 parts by weight, the heat stabilization effect may not be sufficient in the cured product of the heat conductive silicone resin composition, and if it exceeds 20 parts by weight, the thermal conductivity of the heat conductive silicone resin composition may decrease, or problems such as poor dispersion of the heat stabilizer may occur.
  • the thermally conductive silicone resin composition of the present invention is easily prepared by blending the above-mentioned components in a predetermined ratio and mixing them uniformly.
  • the mixing means is not particularly limited, and a known mixer, kneader, etc. can be applied.
  • the uncured thermally conductive silicone resin composition can be cured by leaving it at room temperature or by heating it to promote the crosslinking reaction.
  • the method of adding the surface treatment agent (D) can be a known method such as a method of spraying or immersing the surface treatment agent (D) directly or in a state of being dispersed in a solvent such as an organic solvent onto the thermally conductive filler (C), or a method of mixing the silicone resin component, the thermally conductive filler (C), and the surface treatment agent (D) all at once.
  • the cured product of the thermally conductive silicone resin composition of the present invention has a low-temperature complex modulus change rate of 1000% or less, which is calculated by dividing the absolute value of the difference between the complex modulus at 20 ° C. and -80 ° C. by the complex modulus at 20 ° C.
  • a cured product is obtained that has excellent flexibility under low-temperature conditions, and forms a heat-conducting member in a semiconductor etching apparatus that stably maintains adhesion with a focus ring and a mounting table, prevents a decrease in thermal conductivity, and allows stable plasma etching processing.
  • the complex modulus in this specification is a measured value in a torsional shear mode at 10 Hz. If the low-temperature complex modulus change rate exceeds 1000%, the cured product of the thermally conductive silicone resin composition cannot maintain its flexibility under low-temperature conditions, and cannot follow the deformation caused by the thermal expansion and contraction of the mounting table and focus ring due to temperature changes, and the stability of the state of adhesion with the focus ring and mounting table decreases, which may prevent stable plasma etching processing.
  • the hardness of the cured product of the thermally conductive silicone resin composition of the present invention at room temperature can be set appropriately depending on the application, but from the viewpoint of ease of handling and adhesion to the adherend, it is preferable that the Asker C hardness (based on JIS K6249) is 60 or less, and more preferably an Asker C hardness of 20 to 60.
  • the reason why the hardness is preferably an Asker C hardness of 20 or more is that if the Asker C hardness is less than 20, the cured product of the thermally conductive silicone resin composition may be too soft and difficult to handle.
  • the hardness of the cured product exceeds 60 on the Asker C hardness scale, the ability to conform to the shape of the adherend and the surface irregularities of the adherend tends to decrease, which may reduce good adhesion and increase thermal resistance at the contact interface.
  • the cured product of the thermally conductive silicone resin composition of the present invention functions as a thermally conductive member as described below.
  • the thermal conductivity of the cured product can be set appropriately depending on the application, but since this cured product can be suitably used as a thermally conductive member in a semiconductor etching device, from the viewpoint of preventing a temperature rise in the focus ring during plasma etching processing, the thermal conductivity of the cured product is preferably 1.0 W/m ⁇ K or more, and more preferably 1.5 W/m ⁇ K or more.
  • the thermal conductivity in the present invention is a value measured by a steady-state method in accordance with ASTM D5470, using a sheet of length 10 mm x width 10 mm x thickness 2.0 mm as a test specimen, applying a load of 5 N to the entire surface of the test specimen under conditions where the average temperature of the heating side and cooling side is 50°C.
  • the heat conductive member of the present invention is a cured product of the heat conductive silicone resin composition of the present invention, and is obtained by molding and curing the uncured heat conductive silicone resin composition.
  • the heat conductive member can be used by contacting or placing it close to a heat dissipation target or heat absorption target, and transmitting heat from the target to other members or the environment.
  • the thickness and shape of the heat conductive member can be appropriately set according to the shape and arrangement of the heat sink or other cooling body or the heat generating body such as a CPU, which is the adherend, but it is preferable to make it a thin sheet shape in order to reduce the thermal resistance in the thickness direction.
  • the heat conductive member is produced by molding the uncured heat conductive silicone resin composition into a predetermined shape, leaving the molded product at room temperature or heating it.
  • the uncured composition is supplied onto a substrate film, and then molded into a sheet shape by a known method such as calendar molding, and then heat cured, and the sheet-shaped cured product is cut into a desired shape by a known method such as punching, laser processing, or plotter processing to obtain the heat conductive member.
  • the surface of the heat conductive member of the present invention may be either adhesive or non-adhesive. From the viewpoint of ease of attachment and detachment to the cooling body or heating body, which are the adherends, the surface in contact with the cooling body and the surface in contact with the heating body may have different adhesiveness.
  • Methods for imparting adhesiveness to the surface of the heat conductive member include known methods such as adding a tackifier to a heat conductive silicone resin composition to impart adhesiveness, or applying an adhesive coating to the surface of the heat conductive member.
  • known methods can be applied, such as applying a non-adhesive silicone resin component, or applying a non-adhesive coating or surface modification such as excimer treatment or plasma treatment to the surface of the heat conductive member.
  • the heat conductive member of the present invention can be suitably used as a heat conductive member for a semiconductor etching apparatus. As shown in FIG. 2, the heat conductive member 5 for the semiconductor etching apparatus is sandwiched between the focus ring 3 and the mounting table 2 to form a heat conductive path.
  • the thickness and shape of the heat conductive member 5 can be appropriately set according to the shape and arrangement of the focus ring 3 and the mounting table 2, but it is preferable to make it a thin sheet in order to reduce thermal resistance in the thickness direction.
  • the heat conductive member 5 Since the heat conductive member 5 has excellent flexibility under severe low-temperature conditions, in the semiconductor etching apparatus, the adhesion between the focus ring 3 and the mounting table 2 is stably maintained, the decrease in thermal conductivity is prevented, and stable plasma etching processing can be performed.
  • Thermal conductivity thermal conductivity rate
  • the uncured thermally conductive silicone resin composition was formed into a sheet having a thickness of 2.0 mm by calendar molding, and then preheated in a hot air oven (Tokyo Rikakikai Co., Ltd. WFO-520W) at 70 ° C. for 1 hour, and then heated at 100 ° C. for 3 hours to obtain a sheet-like cured product of the thermally conductive silicone resin composition having a thickness of 2.0 mm.
  • a hot air oven Tokyo Rikakikai Co., Ltd. WFO-520W
  • This sheet-like cured product was cut into a sheet-like test specimen of 10 mm x 10 mm using a Thomson blade die, and a load of 5 N was applied to the entire surface of the test specimen by a steady method in accordance with ASTM D5470, and the thermal conductivity in the thickness direction was measured under conditions where the average temperature of the heating side and the cooling side was 50 ° C., and the average value of the thermal conductivity of the three test specimens was obtained.
  • the measurement device used was a resin material thermal resistance measurement device (manufactured by Hitachi Technology and Services Co., Ltd.). Those with a thermal conductivity of 1 W/m ⁇ K or more were judged to pass ( ⁇ ), and those with a thermal conductivity of less than 1 W/m ⁇ K were judged to fail ( ⁇ ).
  • test specimens were formed by molding each of the uncured thermally conductive silicone resin compositions in the Examples and Comparative Examples into a size of 60 mm length x 60 mm width x 12 mm thickness, preheating at 70°C for 1 hour in a hot air oven (WFO-520W manufactured by Tokyo Rikakikai Co., Ltd.) and then curing by heating at 100°C for 3 hours.
  • a hot air oven WFO-520W manufactured by Tokyo Rikakikai Co., Ltd.
  • the complex modulus at 10 Hz was measured under conditions of a load of 100 g in the range of -80°C to 20°C, and the absolute value of the change in the complex modulus at -80°C (G*1) and at 20°C (G*1-G*0) was divided by the complex modulus at 20°C (G*0) to obtain the value (
  • Test specimens with a low-temperature change rate of 1000% or less were judged as pass ( ⁇ ), and those with a low-temperature change rate of more than 1000% were judged as fail ( ⁇ ).
  • Example 1 A two-liquid addition reaction type silicone gel (SEMICOSIL (registered trademark) 920LT manufactured by Wacker Asahi Kasei Silicone Co., Ltd.) was used as the silicone resin component (I), and liquid A in which a phenyl-modified polyorganosiloxane having vinyl groups at both ends, which is the polyorganosiloxane (A) component, was mixed with a hydrosilylation catalyst (E), and liquid B in which a phenyl-modified hydrogen polyorganosiloxane, which is the hydrogen polyorganosiloxane (B), was mixed with the same polyorganosiloxane (A), were blended in a weight ratio of 58:42 to obtain 100 g of the silicone resin component.
  • SEMICOSIL registered trademark
  • a ternary aluminum oxide powder consisting of 600 g of a first aluminum oxide powder (manufactured by Denka Co., Ltd., DAW-70, average particle size 70 ⁇ m), 300 g of a second aluminum oxide powder (manufactured by Showa Denko K.K., CB-P05, average particle size 5 ⁇ m), and 100 g of a third aluminum oxide powder (manufactured by Sumitomo Chemical Co., Ltd., AA-03F, average particle size 0.2 to 0.4 mm) was prepared as a thermally conductive filler (C).
  • a surface treatment agent (D) for this thermally conductive filler (C) 10 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)) of a dimethylsiloxane-methylphenylsiloxane copolymer (D1) having a trimethoxysilyl group at one end and having a structure in which a phenyl group is bonded to a polysiloxane chain (Tokyo Chemical Industry Co., Ltd., Z5804, viscosity 30 mPa s, dimethylsiloxane 88-94%, methylphenylsiloxane 6-12%) was prepared.
  • the silicone resin component 100 g of the silicone resin component, 1000 g of the thermally conductive filler (C), and 10 g of the surface treatment agent (D) were charged into a planetary mixer (ACM-5LVT manufactured by Aikosha Seisakusho Co., Ltd.), mixed at 150 rpm for 10 minutes under atmospheric pressure, and further mixed at 150 rpm for 10 minutes under reduced pressure conditions of -0.1 MPa, and the mixture was degassed under reduced pressure to obtain an uncured thermally conductive silicone resin composition of Example 1.
  • the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 2 An uncured thermally conductive silicone resin composition of Example 2 was obtained in the same manner as in Example 1, except that the amount of thermally conductive filler (C) used in Example 1 was changed to 500 g of a ternary aluminum oxide powder consisting of 300 g of the first aluminum oxide powder, 150 g of the second aluminum oxide powder, and 50 g of the third aluminum oxide powder, and the amount of surface treatment agent (D1) used in Example 1 was changed to 5 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 3 An uncured thermally conductive silicone resin composition of Example 3 was obtained in the same manner as in Example 1, except that the amount of thermally conductive filler (C) used in Example 1 was changed to 1500 g of a ternary aluminum oxide powder consisting of 900 g of the first aluminum oxide powder, 450 g of the second aluminum oxide powder, and 150 g of the third aluminum oxide powder, and the amount of surface treatment agent (D1) used in Example 1 was changed to 15 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 4 An uncured thermally conductive silicone resin composition of Example 4 was obtained in the same manner as in Example 1, except that the amount of thermally conductive filler (C) used in Example 1 was changed to 2000 g of a ternary aluminum oxide powder consisting of 1200 g of the first aluminum oxide powder, 600 g of the second aluminum oxide powder, and 200 g of the third aluminum oxide powder, and the amount of surface treatment agent (D1) used in Example 1 was changed to 20 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 5 An uncured thermally conductive silicone resin composition of Example 5 was obtained in the same manner as in Example 1, except that the amount of thermally conductive filler (C) used in Example 1 was changed to 2200 g of a ternary aluminum oxide powder consisting of 1320 g of the first aluminum oxide powder, 660 g of the second aluminum oxide powder, and 220 g of the third aluminum oxide powder, and the amount of surface treatment agent (D1) used in Example 1 was changed to 22 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 6 An uncured thermally conductive silicone resin composition of Example 6 was obtained in the same manner as in Example 1, except that the amount of the surface treatment agent (D1) used in Example 1 was changed to 5 g (0.5 parts by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 7 An uncured thermally conductive silicone resin composition of Example 7 was obtained in the same manner as in Example 1, except that the amount of the surface treatment agent (D1) used in Example 1 was changed to 20 g (2.0 parts by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 8 An uncured thermally conductive silicone resin composition of Example 8 was obtained in the same manner as in Example 1, except that the surface treatment agent (D1) used in Example 1 was replaced with a polyorganosiloxane (D2) containing a trialkoxysilyl group at one end (manufactured by Shin-Etsu Chemical Co., Ltd., X24-9011, no phenyl group bond in the polysiloxane chain).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 9 An uncured thermally conductive silicone resin composition of Example 9 was obtained in the same manner as in Example 8, except that the amount of thermally conductive filler (C) used in Example 8 was changed to 500 g of a ternary aluminum oxide powder consisting of 300 g of the first aluminum oxide powder, 150 g of the second aluminum oxide powder, and 50 g of the third aluminum oxide powder, and the amount of surface treatment agent (D2) used in Example 8 was changed to 5 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 10 An uncured thermally conductive silicone resin composition of Example 10 was obtained in the same manner as in Example 8, except that the amount of thermally conductive filler (C) used in Example 8 was changed to 1200 g of a ternary aluminum oxide powder consisting of 720 g of the first aluminum oxide powder, 360 g of the second aluminum oxide powder, and 120 g of the third aluminum oxide powder, and the amount of surface treatment agent (D2) used in Example 8 was changed to 12 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 11 An uncured thermally conductive silicone resin composition of Example 11 was obtained in the same manner as in Example 8, except that the amount of thermally conductive filler (C) used in Example 8 was changed to 1500 g of a ternary aluminum oxide powder consisting of 900 g of the first aluminum oxide powder, 450 g of the second aluminum oxide powder, and 150 g of the third aluminum oxide powder, and the amount of surface treatment agent (D2) used in Example 8 was changed to 15 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 12 An uncured thermally conductive silicone resin composition of Example 12 was obtained in the same manner as in Example 8, except that the amount of thermally conductive filler (C) used in Example 8 was changed to 1800 g of a ternary aluminum oxide powder consisting of 1080 g of the first aluminum oxide powder, 540 g of the second aluminum oxide powder, and 180 g of the third aluminum oxide powder, and the amount of surface treatment agent (D2) used in Example 8 was changed to 18 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 13 An uncured thermally conductive silicone resin composition of Example 13 was obtained in the same manner as in Example 9, except that the amount of the surface treatment agent (D2) used in Example 9 was 2.5 g (0.5 parts by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 14 An uncured thermally conductive silicone resin composition of Example 14 was obtained in the same manner as in Example 9, except that the amount of the surface treatment agent (D2) used in Example 9 was 10 g (2.0 parts by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 15 An uncured thermally conductive silicone resin composition of Example 15 was obtained in the same manner as in Example 1, except that the amount of thermally conductive filler (C) used in Example 1 was changed to 320 g of a ternary aluminum oxide powder consisting of 192 g of the first aluminum oxide powder, 96 g of the second aluminum oxide powder, and 32 g of the third aluminum oxide powder, and the amount of surface treatment agent (D1) used in Example 1 was changed to 3.2 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Comparative Example 1 An uncured thermally conductive silicone resin composition of Comparative Example 1 was obtained in the same manner as in Example 1, except that the amount of thermally conductive filler (C) used in Example 1 was changed to 200 g of a ternary aluminum oxide powder consisting of 120 g of the first aluminum oxide powder, 60 g of the second aluminum oxide powder, and 20 g of the third aluminum oxide powder, and the amount of surface treatment agent (D1) used in Example 1 was changed to 2 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Comparative Example 2 An uncured thermally conductive silicone resin composition of Comparative Example 2 was obtained in the same manner as in Example 1, except that the amount of thermally conductive filler (C) used in Example 1 was changed to 2500 g of a ternary aluminum oxide powder consisting of 1500 g of the first aluminum oxide powder, 750 g of the second aluminum oxide powder, and 250 g of the third aluminum oxide powder, and the amount of surface treatment agent (D1) used in Example 1 was changed to 25 g (1.0 part by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Example 3 As the silicone resin component (II) according to this comparative example, the A liquid of the two-liquid addition reaction type silicone gel (CF5106 manufactured by Dow Corning Toray Co., Ltd.) and the B liquid of the two-liquid addition reaction type silicone gel (SEMICOSIL920LT manufactured by Wacker Asahi Kasei Silicone Co., Ltd.) used in Example 2 were used.
  • the A liquid of the two-liquid addition reaction type silicone gel (CF5106 manufactured by Dow Corning Toray Co., Ltd.) contains a polyorganosiloxane component (component a) having vinyl groups at both ends and a hydrosilylation catalyst (E) mixed therein, but this polyorganosiloxane component (component a) does not have a phenyl group in the molecule and is a polyorganosiloxane that has not been phenyl-modified.
  • This A liquid and the B liquid of the two-liquid addition reaction type silicone gel used in Example 2 were mixed in a weight ratio of 50:50 to obtain 100 g of silicone resin component (II). Except for this, the uncured thermally conductive silicone resin composition of Comparative Example 3 was obtained in the same manner as in Example 2. With respect to this thermally conductive silicone resin composition, the above-mentioned (1) to (3) physical properties were measured and the effects were evaluated.
  • the B liquid of the two-liquid addition reaction type silicone gel (CF5106 manufactured by Toray Dow Corning Co., Ltd.) is a mixture of a hydrogen polyorganosiloxane (component b) that does not have a phenyl group in the molecule and is not phenyl-modified, and a polyorganosiloxane (component a) that is not phenyl-modified and has vinyl groups at both ends.
  • the A liquid of the two-liquid addition reaction type silicone gel used in Example 2 and this B liquid were mixed in a weight ratio of 50:50 to obtain 100 g of silicone resin component (III). Except for this, the uncured thermally conductive silicone resin composition of Comparative Example 4 was obtained in the same manner as in Example 2. With respect to this thermally conductive silicone resin composition, the above-mentioned (1) to (3) physical properties were measured and the effects were evaluated.
  • Comparative Example 6 An uncured thermally conductive silicone resin composition of Comparative Example 6 was obtained in the same manner as in Example 1, except that the amount of thermally conductive filler (C) used in Example 1 was changed to 1800 g of a ternary aluminum oxide powder consisting of 1080 g of the first aluminum oxide powder, 540 g of the second aluminum oxide powder, and 180 g of the third aluminum oxide powder, and the amount of surface treatment agent (D1) used in Example 1 was changed to 3.6 g (0.2 parts by weight per 100 parts by weight of the total amount of the thermally conductive filler (C)).
  • the thermally conductive silicone resin composition the physical properties (1) to (3) described above were measured and the effects were evaluated.
  • Comparative Example 7 An uncured thermally conductive silicone resin composition of Comparative Example 7 was obtained in the same manner as in Example 1, except that the surface treatment agent (D1) used in Example 1 was replaced with n-decyltrimethoxysilane (D3) (DOWSIL Z-6210 Silane, manufactured by Dow Toray Co., Ltd.).
  • D3 n-decyltrimethoxysilane
  • Example 1 to 15 shown in Tables 1 and 2 reveal that the thermally conductive silicone resin composition having the configuration of the present invention has physical properties such that the hardness of the cured product is 60 or less on the Asker C hardness scale and the thermal conductivity is 1.0 W/m ⁇ K or more, and that it has excellent room temperature flexibility and thermal conductivity.
  • the low-temperature change rate of the complex modulus calculated by dividing the absolute value of the difference between the complex modulus of the cured product at 20°C and -80°C by the complex modulus of the cured product at 20°C, is 1000% or less, demonstrating excellent low-temperature flexibility.
  • the surface treatment agent (D) is a phenyl-modified one-terminus trialkoxysilyl group-containing polyorganosiloxane (D1) in which a phenyl group is bonded to a polysiloxane chain, or an unphenyl-modified one-terminus trialkoxysilyl group-containing polyorganosiloxane (D2).
  • the low-temperature change rate is further reduced compared to the case where the unphenyl-modified one-terminus trialkoxysilyl group-containing polyorganosiloxane (D2) is used, and a thermally conductive silicone resin composition that can form a thermally conductive member with even improved flexibility under low-temperature conditions can be obtained.
  • the results of Comparative Examples 1 to 8 shown in Table 3 show that the effects of the present invention cannot be obtained with a thermally conductive silicone resin composition that does not have the configuration of the present invention.
  • the results of Comparative Example 1 show that when the amount of thermally conductive filler (C) was 200 parts by weight relative to 100 parts by weight of the silicone resin component, the thermal conductivity was significantly reduced to 0.7 W/m ⁇ K.
  • the results of Comparative Example 2 show that when the amount of thermally conductive filler (C) was 2,500 parts by weight relative to 100 parts by weight of the silicone resin component, the amount of the silicone resin component was too small to be molded and evaluation was not possible.
  • Comparative Examples 3 to 5 show that when at least one of the polyorganosiloxane (A) and hydrogen polyorganosiloxane (B) constituting the silicone resin component is not phenyl-modified, the low-temperature flexibility of the cured product is significantly reduced, and therefore it is important in the present invention that both the (A) and (B) components constituting the silicone resin component have phenyl groups.
  • Comparative Example 6 show that when the blending ratio of the surface treatment agent (D) to 100 parts by weight of the total weight of the thermally conductive filler (C) is less than 0.5 parts by weight, the affinity between the thermally conductive filler (C) and the silicone resin component is insufficient, and when compared with conditions (Example 4) or similar conditions (Example 12) where the blending ratio of the thermally conductive filler (C) is the same, the hardness of the cured product increases and the room temperature flexibility decreases, as well as the low temperature flexibility decreases.
  • Comparative Example 7 show that when the silane-based surface treatment agent n-decyltrimethoxysilane (D3) was used as the surface treatment agent (D) instead of the polyorganosiloxane containing a trialkoxysilyl group at one end (D1), the low-temperature flexibility of the cured product of the thermally conductive silicone resin composition was significantly reduced. From the above, it was found that the configuration of the present invention is important in order to achieve flexibility and high thermal conductivity of the cured product (thermal conductive member) under severe low-temperature conditions.
  • the thermally conductive silicone resin composition of the present invention can form a cured product (thermally conductive material) that has both excellent flexibility and high thermal conductivity under low-temperature conditions, making it useful in a wide range of industries, including the semiconductor etching process, electronic devices that require heat dissipation measures, and devices used in outer space or in extremely cold regions.
  • Substrate mounting unit Mounting table (lower electrode unit) 2a Chuck mechanism (wafer chuck, etc.) 2b Support stand 3 Focus ring (edge ring) 4 Cooling unit 5 Heat conductive member W Substrate to be processed (wafer, etc.)

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Abstract

L'invention concerne une composition de résine de silicone thermoconductrice capable de former un article durci ayant à la fois une flexibilité et une conductivité thermique élevée dans des conditions de basse température même lorsqu'un niveau élevé de charge thermoconductrice est ajouté.　Une composition de résine de silicone thermoconductrice selon la présente invention comprend un composant de résine de silicone contenant (A) un polyorganosiloxane ayant des groupes alcényle au moins aux deux extrémités, (B) un polyorganosiloxane d'hydrogène ayant au moins un atome d'hydrogène lié à un atome de silicium dans une molécule et (E) un catalyseur d'hydrosilylation, (C) une charge thermoconductrice et (D) un agent de traitement de surface pour le traitement de surface de la charge thermoconductrice (C). Le composant (A) est un polyorganosiloxane modifié par phényle ayant au moins un groupe phényle dans la molécule. Le composant (B) est un polyorganosiloxane hydrogène modifié par phényle ayant au moins un groupe phényle dans la molécule. La proportion du composant (C) ajouté est de 300 à 2 200 parties en poids par rapport à 100 parties en poids du composant de résine de silicone. Le composant (D) est un polyorganosiloxane hydrolysable à une extrémité ayant un groupe hydrolysable lié à un atome de silicium à une extrémité et la proportion du composant (D) ajouté est de 0,5 à 2 parties en poids par rapport à 100 parties en poids du composant (C). Un article durci de la composition de résine de silicone thermoconductrice présente un taux de changement de module complexe à basse température de 1 000% ou moins tel que déterminé par division de la valeur absolue de la différence de module complexe entre 20°C et -80°C par le module complexe à 20°C.
PCT/JP2024/007724 2023-03-06 2024-03-01 Composition de résine de silicone thermoconductrice et élément thermoconducteur Pending WO2024185675A1 (fr)

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JP2014145024A (ja) * 2013-01-29 2014-08-14 Taika:Kk 耐熱性に優れた熱伝導性樹脂組成物およびそれを用いた放熱部品
JP2017039800A (ja) * 2015-08-17 2017-02-23 積水化学工業株式会社 半導体素子保護用材料及び半導体装置
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