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WO2024062923A1 - Film, stratifié, appareil de traitement au plasma et procédé de fabrication de stratifié - Google Patents

Film, stratifié, appareil de traitement au plasma et procédé de fabrication de stratifié Download PDF

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Publication number
WO2024062923A1
WO2024062923A1 PCT/JP2023/032488 JP2023032488W WO2024062923A1 WO 2024062923 A1 WO2024062923 A1 WO 2024062923A1 JP 2023032488 W JP2023032488 W JP 2023032488W WO 2024062923 A1 WO2024062923 A1 WO 2024062923A1
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Prior art keywords
film
less
group
compound
mass ppm
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English (en)
Japanese (ja)
Inventor
勇剛 谷垣
彰 嶋田
大作 田中
庸平 酒部
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Toray Industries Inc
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Toray Industries Inc
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Priority to CN202380066626.XA priority Critical patent/CN119894987A/zh
Priority to JP2023555260A priority patent/JPWO2024062923A1/ja
Priority to KR1020257007634A priority patent/KR20250069538A/ko
Publication of WO2024062923A1 publication Critical patent/WO2024062923A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/013—Fillers, pigments or reinforcing 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H10P72/70—
    • H10P72/722—
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to a film, a laminate, a plasma processing apparatus, and a method for manufacturing a laminate.
  • electrostatic chucks are used as a means to attract and hold semiconductor wafers, glass substrates, etc. in substrate processing equipment that performs sputtering, vapor deposition, chemical vapor deposition, ion implantation, etching, ashing, exposure, or inspection in semiconductor manufacturing processes.
  • a plasma processing apparatus is provided with a mounting table on which a semiconductor wafer is placed inside a vacuum chamber, and the mounting table mainly includes an electrostatic chuck and a cooler that controls the temperature of the electrostatic chuck.
  • An electrostatic chuck is manufactured by sandwiching an electrode between ceramic dielectric members and firing them, and includes a base member, a ceramic dielectric member made of ceramic, and an adhesive member that adheres the base member and the ceramic dielectric member. We are prepared.
  • An electrostatic chuck is a holding device that attracts and holds a semiconductor wafer or the like on the surface of a ceramic dielectric member using electrostatic attraction generated by applying a voltage to a built-in electrode.
  • adhesive members in electrostatic chucks and the like include silicone resin-based adhesive members and acrylic resin-based adhesive members (see, for example, Patent Document 2 or Patent Document 3).
  • Patent No. 6621882 Japanese Patent Application Publication No. 2011-151280 Japanese Patent Application Publication No. 2014-207374
  • An object of the present invention is to provide a film that has excellent adhesion between members even at extremely low temperatures of about -50°C and has high thermal cycle reliability.
  • the film of the present invention has the following configurations [1] to [20].
  • a film containing (SA) a binder resin and (SD) a thermally conductive filler includes (SD1) a first thermally conductive filler and (SD2) a second thermally conductive filler,
  • the (SD1) first thermally conductive filler has an average primary particle diameter of 1.0 to 200 ⁇ m
  • the average primary particle diameter of the (SD2) second thermally conductive filler is 0.010 ⁇ m or more and less than 1.0 ⁇ m
  • Shear strain at -50°C is 0.70 to 20
  • [4] The film according to any one of [1] to [3], which satisfies at least one of the following conditions (S4a) and (S4b).
  • S4a The content of platinum element in the film is 1,000 mass ppm or less
  • S4b The total content of ions containing platinum element in the film is 5,000 mass ppm or less.
  • [5] The film according to any one of [1] to [4], which satisfies at least one of the following conditions (S5a) and (S5b).
  • S5a The total content of organosilane compounds having 1 to 2 silicon atoms in the film is 1,000 mass ppm or less
  • S5b The total content of cyclic silicone compounds in the film is 1,000 mass ppm or less .
  • the elastic modulus at -50°C is 0.10 to 200 MPa
  • the resin containing a silicone structure and/or siloxane structure in the structural unit of the resin (SA1) is selected from the group consisting of an imide structure, an amide structure, and an oxazole structure in the structural unit of the resin (SA1-1).
  • the resin containing one or more types selected from the group consisting of an imide structure, an amide structure, and an oxazole structure in the structural unit of the resin (SA1-1) has the following residues (1) and (2).
  • [15] Contains an (SB) epoxy compound or a compound having a structure derived from an epoxy compound (hereinafter referred to as "(SB) compound"),
  • the (SB) compound is (SB1) a compound having a structure containing an oxyalkylene group, (SB2) a compound having a structure containing at least two aromatic structures and a structure containing an oxyalkylene group, and (SB2) a compound having a structure containing at least two aromatic structures and containing an oxyalkylene group; SB3) A compound having a tertiary amine structure that binds to an arylene group and two divalent organic groups. film.
  • [16] Contains an (SC) amine compound or a compound having a structure derived from an amine compound (hereinafter referred to as "(SC) compound"),
  • the (SC) compound contains (SC1) a compound having a silicone structure and/or a siloxane structure and having at least two alkylene groups bonded to silicon atoms in the silicone structure and/or the siloxane structure.
  • SC1 a compound having a silicone structure and/or a siloxane structure and having at least two alkylene groups bonded to silicon atoms in the silicone structure and/or the siloxane structure.
  • a laminate comprising a base member, the film according to any one of [1] to [19] above, and a ceramic dielectric member in this order, A laminate in which the base member and the ceramic dielectric member have different coefficients of thermal expansion.
  • a plasma processing apparatus comprising a plasma generation source and the laminate according to [20] or [21].
  • a method for manufacturing a laminate comprising the steps of arranging a base member, arranging the film according to any one of [1] to [19] above, and arranging a ceramic dielectric member.
  • FIG. 1 is a schematic cross-sectional view showing Embodiment 1 of a laminate, which is a laminate including a first support, a film, and a second support.
  • 11 is a schematic cross-sectional view showing a laminate according to a second embodiment of the present invention, which is a laminate having a base member, a film, and a ceramic dielectric member.
  • the film of the present invention will be described below. Note that when describing the film of the present invention, the description is common to the first and second embodiments of the film of the present invention. On the other hand, when describing a film of a specific embodiment, it will be described as a first embodiment of the film of the present invention. However, the present invention is not limited only to the following embodiments, and various changes can be made without departing from the gist of the invention and which can achieve the purpose of the invention.
  • the main chain of a resin refers to the longest chain among the chains that make up the resin, including structural units.
  • the side chain of a resin refers to a chain that branches off from the main chain or is bonded to the main chain, among the chains that make up the resin, including structural units, and that is shorter than the main chain.
  • the end of a resin refers to a structure that seals the main chain, such as a structure derived from an end-capping agent.
  • overlapping refers to directly or indirectly overlapping in the z-axis direction. That is, when a certain layer and another layer overlap, those layers may be in contact with each other, or another layer may exist between those layers.
  • the silicone structure refers to a structure that has a main skeleton of Si--O--Si bonds and two organic groups on a silicon atom. That is, the silicon atom in the silicone structure is bonded to two organic groups and two oxygen atoms.
  • the siloxane structure refers to a structure having a main skeleton of Si--O--Si bonds and one organic group on a silicon atom. That is, the silicon atom in the siloxane structure is bonded to one organic group and three oxygen atoms.
  • a first aspect of the film of the present invention is a film containing (SA) a binder resin and (SD) a thermally conductive filler
  • the (SD) thermally conductive filler includes (SD1) a first thermally conductive filler and (SD2) a second thermally conductive filler, and the average primary particle diameter of the (SD1) first thermally conductive filler. is 1.0 to 200 ⁇ m, the average primary particle diameter of the second thermally conductive filler (SD2) is 0.010 ⁇ m or more and less than 1.0 ⁇ m, and the shear strain at -50°C is 0.70 to 200 ⁇ m. 20 and has a thermal conductivity of 0.10 to 5.0 W/(m ⁇ K) at 25°C.
  • the present invention can provide a film that has excellent adhesion between members even at extremely low temperatures of about -50° C. and has high thermal cycle reliability. This is because the slope of the stress-strain curve, where the vertical axis is stress and the horizontal axis is strain, decreases (strain per unit stress increases) due to the anchoring effect of the filler with a specific average primary particle diameter. This is thought to be because the shear strain can be adjusted within a specific range. Therefore, due to high shear strain at extremely low temperatures of around -50°C, the film has the flexibility to alleviate the difference in thermal expansion coefficient between the parts it joins, improving its ability to follow each part. It is estimated that adhesion and cooling/heating cycle reliability are improved.
  • the film contains two types of thermally conductive fillers with specific average primary particle diameters, it is possible to efficiently radiate heat generated in the parts to be joined, reducing internal stress caused by temperature rise in the parts. It is also possible that this is due to the reason. In addition, it is also presumed that the heat stored in the film can be reduced, and changes in mechanical properties due to temperature increases in the film can be suppressed.
  • film refers to a film that can form a free-standing film with a single layer.
  • the film preferably has adhesive properties, and is also preferably made by bonding multiple components.
  • a free-standing film with a single layer refers to a film that can be formed without a support, with a width of 5.0 cm or more, a length of 5.0 cm or more, and a thickness of 5.0 ⁇ m or more.
  • a second aspect of the film of the present invention is a film containing (SA) a binder resin and (SD) a thermally conductive filler, which has an elastic modulus of 0.10 to 200 MPa at -50°C, and has an elastic modulus of 0.10 to 200 MPa at 25°C.
  • the film has a thermal conductivity of 0.10 to 5.0 W/(m ⁇ K).
  • the present invention can provide a film that has excellent adhesion between members even at extremely low temperatures of about -50°C and has high thermal cycle reliability.
  • the elastic modulus By lowering the elastic modulus at extremely low temperatures of around -50°C, it is possible to reduce the internal stress caused by the difference in thermal expansion coefficient between the parts that the film joins, and improve the ability to follow each part, resulting in better adhesion. It is presumed that the cooling and heating cycle reliability will be improved.
  • the film of the present invention contains a (SA) binder resin.
  • the binder resin is a heat-resistant resin that at least partially remains in the cured product obtained by curing the composition for forming the film of the present invention.
  • the (SA) binder resin is preferably a resin that forms or has formed a crosslinked structure with the (SB) compound described below.
  • the crosslinked structure is preferably formed by reaction, and is not particularly limited, and may be formed by heating, irradiation with energy rays, etc.
  • the binder resin preferably has an acidic group or a structure derived from an acidic group, and more preferably has an acidic group or a structure derived from an acidic group in the repeating unit of the resin.
  • the above acidic group is a phenolic hydroxyl group, hydroxyimide group, hydroxyamide group, silanol group, 1,1-bis(trifluoromethyl)methylol group, mercapto group, carboxy group, carboxylic acid anhydride group, or sulfonic acid group.
  • a phenolic hydroxyl group, a carboxy group, or a carboxylic acid anhydride group is more preferable.
  • the acidic group is preferably a phenolic hydroxyl group, a hydroxyimide group, a hydroxyamide group, a silanol group, a mercapto group, a carboxy group, a carboxylic acid anhydride group, or a sulfonic acid group.
  • the acid equivalent of the (SA) binder resin is preferably 200 g/mol or more, more preferably 250 g/mol or more, and even more preferably 300 g/mol or more, from the viewpoint of improving adhesion and improving cooling/heating cycle reliability.
  • it is preferably 600 g/mol or less, more preferably 500 g/mol or less, and even more preferably 450 g/mol or less.
  • the (SA) binder resin having the above acidic group or a structure derived from an acidic group adjusts the shear strain at -50°C within the range of 0.70 to 20 by forming a crosslinked structure with the (SB) compound described below. And/or it is suitable for adjusting the elastic modulus at -50°C within the range of 0.10 to 200 MPa. Further, the above acidic group or the structure derived from the acidic group can improve the dispersibility of the filler through interaction with the thermally conductive filler (SD) described later, and the effect of improving the thermal conductivity of the film becomes remarkable. It is estimated that these improve the followability to each member, thereby improving the adhesion and the reliability of cooling/heating cycles.
  • SD thermally conductive filler
  • SA binder resin is a resin containing silicone structure and/or siloxane structure in the structural unit of (SA1) resin (hereinafter referred to as , "(SA1) resin").
  • SA1 The silicone structure and siloxane structure of the resin are bonded to at least two alkylene groups, and are preferably divalent or higher-valent structures via these alkylene groups.
  • the above bivalent or higher valence structure is more preferably trivalent or higher, and even more preferably tetravalent or higher.
  • the above-mentioned structure having a valence of 2 or more is preferably 6 or less.
  • the number of silicon atoms in the silicone structure and/or siloxane structure in the resin is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, and particularly preferably 20 or more. On the other hand, the number of silicon atoms is preferably 30 or less, more preferably 27 or less, and even more preferably 25 or less.
  • the silicone structure is preferably a dialkyl silicone structure and/or a monoalkyl silicone structure
  • the siloxane structure is preferably a monoalkyl siloxane structure
  • the number of carbon atoms in the alkyl group that the dialkyl silicone structure and monoalkyl silicone structure have is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.
  • the number of carbon atoms in the alkyl group is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • the number of carbon atoms in the alkyl group that the monoalkylsiloxane structure has is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.
  • the number of carbon atoms in the alkyl group is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • the content ratio of the aliphatic group to the total of aliphatic groups and aromatic groups bonded to silicon atoms in the silicone structure and/or siloxane structure improves adhesion and cooling/heating cycle reliability. From this viewpoint, it is preferably 80 mol% or more, more preferably 85 mol% or more, and even more preferably 90 mol% or more.
  • the content ratio of the aliphatic group to the total of the aliphatic group and aromatic group is preferably 100 mol% or less, more preferably 99 mol% or less, and 97 mol% or less from the viewpoint of improving the reliability of the cooling/heating cycle. More preferred.
  • the aliphatic group contained in the resin is preferably an alkyl group.
  • the preferred number of carbon atoms in the alkyl group is also the same as above.
  • the alkyl group is preferably a methyl group, ethyl group, propyl group, butyl group, or hexyl group.
  • SA1 The number of carbon atoms in the aromatic group contained in the resin is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more. On the other hand, the number of carbon atoms in the aromatic group is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less.
  • the aromatic group is preferably a phenyl group, tolyl group, xylyl group, phenoxy group, tolyloxy group, or xylyloxy group.
  • SA1 resin has a flexible skeleton derived from a silicone structure or a siloxane structure, and has a shear strain at -50°C adjusted to within a range of 0.70 to 20 and/or an elastic modulus at -50°C. This is suitable for adjusting the pressure within the range of 0.10 to 200 MPa.
  • the resin consists of an imide structure, an amide structure, and an oxazole structure in the structural unit of the resin (SA1-1) from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving cooling and heating cycle reliability. It is preferable to contain a resin "hereinafter referred to as (SA1-1) resin" containing one or more types selected from the group.
  • the resin consists of an imide structure, an amide structure, and an oxazole structure in the structural unit of the resin, such as polyimide, polybenzoxazole, their precursors, and copolymers made of two or more of them. It is a resin containing one or more types selected from the group.
  • resins include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, polyamide, and their like. It is preferable to contain one or more types selected from the group consisting of copolymers of two or more types (hereinafter referred to as "polyimide resins").
  • polyimide resins The resin may be a single resin or a copolymer thereof.
  • the resin preferably has one or more types selected from the group consisting of the following residues (1) and (2).
  • a silicone structure and/or a siloxane structure Tetracarboxylic acid residue, tetracarboxylic acid derivative residue, tricarboxylic acid residue, tricarboxylic acid derivative residue, dicarboxylic acid residue, or dicarboxylic acid derivative residue.
  • SA1-1 The residue of the above (1) that the resin has is a diamine residue containing a silicone structure and/or a siloxane structure, a diamine derivative residue containing a silicone structure and/or a siloxane structure, a silicone structure and/or a siloxane structure.
  • SA1-1 The residue in (2) above that the resin has is (2) a tetracarboxylic acid residue containing a silicone structure and/or a siloxane structure, a tetracarboxylic acid derivative residue containing a silicone structure and/or a siloxane structure. , a tricarboxylic acid residue containing a silicone structure and/or a siloxane structure, a tricarboxylic acid derivative residue containing a silicone structure and/or a siloxane structure, a dicarboxylic acid residue containing a silicone structure and/or a siloxane structure, or a silicone structure and/or It is a dicarboxylic acid derivative residue containing a siloxane structure.
  • the residue of (1) above that the resin has is divalent or higher, preferably trivalent or higher.
  • the residue in (1) above preferably has a valence of 6 or less, more preferably a valence of 4 or less.
  • the residue (2) mentioned above in the resin (SA1-1) has a valence of two or more, preferably a valence of three or more, and more preferably a valence of four or more.
  • the residue in (2) above is preferably hexavalent or less.
  • the residue of the above (2) that the resin has is a tetracarboxylic dianhydride residue, a tricarboxylic acid anhydride residue, or a dicarboxylic acid anhydride residue containing a silicone structure and/or a siloxane structure. is preferred. Further, the residue in (2) above preferably has an acid anhydride residue containing a phthalic acid structure, an acid anhydride residue containing a succinic acid structure, or an acid anhydride residue containing a maleic acid structure.
  • the total content ratio of the residues in (1) above and the residues in (2) above in the total of all amine residues and all carboxylic acid residues is From the viewpoint of improving adhesion at low temperatures and improving thermal cycle reliability, it is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
  • the total content ratio of the residues in (1) above and the residues in (2) above in the total of all amine residues and all carboxylic acid residues should be 100 mol% or less from the viewpoint of improving cooling/heating cycle reliability. is preferable, 99 mol% or less is more preferable, and even more preferably 97 mol% or less.
  • the total content ratio of the residues in (1) above to all amine residues is determined from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving cooling and heating cycle reliability. It is preferably at least 10 mol%, more preferably at least 30 mol%, even more preferably at least 40 mol%, even more preferably at least 60 mol%, particularly preferably at least 80 mol%.
  • the total content ratio of the residues in (1) above in all amine residues is preferably 100 mol% or less, more preferably 99 mol% or less, and even more preferably 97 mol% or less, from the viewpoint of improving cooling/heating cycle reliability. .
  • the total content ratio of the residues in (2) above to the total carboxylic acid residues is determined from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving cooling and heating cycle reliability. , is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
  • the total content ratio of the residues in (2) above in all carboxylic acid residues is preferably 100 mol% or less, more preferably 99 mol% or less, and even more preferably 97 mol% or less, from the viewpoint of improving cooling/heating cycle reliability. preferable.
  • X 1 to X 4 each independently represent a direct bond, an oxygen atom, an alkylene group having 1 to 30 carbon atoms, an alkyleneoxy group having 1 to 30 carbon atoms, or an arylene group having 6 to 30 carbon atoms.
  • Y 1 and Y 2 each independently represent a trivalent organic group having 1 to 20 carbon atoms.
  • R 21 to R 32 each independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms.
  • x and y each independently represent an integer of 1 to 100.
  • * 1 to * 8 each independently represent a bonding point with another structure.
  • the trivalent organic group having 1 to 20 carbon atoms is preferably a trivalent hydrocarbon group having 1 to 20 carbon atoms.
  • the alkyl group having 1 to 30 carbon atoms is preferably a methyl group, ethyl group, propyl group, butyl group, or hexyl group.
  • the aryl group having 6 to 30 carbon atoms is preferably a phenyl group, tolyl group, or xylyl group.
  • the aryloxy group having 6 to 30 carbon atoms is preferably a phenoxy group, tolyloxy group, or xylyloxy group.
  • the alkylene group having 1 to 30 carbon atoms is preferably a methylene group, ethylene group, propylene group, butylene group, or hexylene group.
  • the arylene group having 6 to 30 carbon atoms is preferably a phenylene group, tolylene group, or xylylene group. Note that the alkyl group and alkylene group have a linear structure or a branched structure.
  • the above alkyl group, aryl group, aryloxy group, alkylene group, and arylene group may have a heteroatom and may be unsubstituted or substituted.
  • x is preferably 6 or more, more preferably 15 or more, even more preferably 24 or more, even more preferably 28 or more, and even more preferably 32 or more, from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving cooling/heating cycle reliability. Particularly preferred. On the other hand, x is preferably 100 or less, more preferably 70 or less, even more preferably 50 or less, particularly preferably 44 or less, from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving cooling/heating cycle reliability.
  • y is preferably 6 or more, more preferably 11 or more, even more preferably 15 or more, and particularly preferably 18 or more.
  • y is preferably 100 or less, more preferably 50 or less, even more preferably 30 or less, and particularly preferably 26 or less, from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving cooling/heating cycle reliability.
  • the total content ratio of structures in which x is 6 or more and 100 or less is from the viewpoint of the effect, the content is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more.
  • the total content ratio of structures in which x is 6 or more and 100 or less is preferably 100 mol% or less, and 99 mol% or less, from the viewpoint of the effects of the above invention. is more preferable, and even more preferably 97 mol% or less.
  • the total content ratio of structures in which y is 6 or more and 100 or less is from the viewpoint of the effect, the content is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more.
  • the total content ratio of structures in which y is 6 or more and 100 or less is preferably 100 mol% or less, and 99 mol% or less, from the viewpoint of the effects of the above invention. is more preferable, and even more preferably 97 mol% or less.
  • the (SA1-1) resin as described above has a flexible skeleton derived from a silicone structure or siloxane structure, and due to the improved mechanical properties due to the imide structure, amide structure, or oxazole structure, it is suitable for adjusting the shear strain at -50°C to within the range of 0.70 to 20, and/or adjusting the elastic modulus at -50°C to within the range of 0.10 to 200 MPa. Furthermore, due to the coordination ability with each component derived from the imide structure, amide structure, or oxazole structure, the (SA1-1) resin is thought to function as an anchor at the interface with the component at extremely low temperatures. This is presumably why the conformability to each component is improved, and the adhesion and thermal cycle reliability are improved.
  • SA1-1 As the amine monomer for introducing the residue of (1) above into the resin, for example, X-22-161A (amino group equivalent: 800 g/ mol), X-22-161B (amino group equivalent: 1,500 g/mol), KF-8012 (amino group equivalent: 2,200 g/mol), KF-8010 (amino group equivalent: 430 g/mol), or KF -8008 (amino group equivalent: 5,700 g/mol) (both manufactured by Shin-Etsu Chemical Co., Ltd.), or X-22-1660B-3 (amino group equivalent: 2, 200 g/mol) or X-22-9409 (amino group equivalent: 650 g/mol) (both manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Examples of the acid monomer for introducing the residue (2) above into the resin include X-22-168AS (acid anhydride group equivalent: 500 g/mol), X-22- 168A (acid anhydride group equivalent: 1,000 g/mol), X-22-168B (acid anhydride group equivalent: 1,600 g/mol), or X-22-168-P5-B (acid anhydride group equivalent :2,100g/mol) (both manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the resin preferably has a residue having an acidic group or a structure derived from an acidic group, and the resin preferably has a residue having an acidic group or a structure derived from an acidic group in the repeating unit of the resin. It is more preferable to have a residue having the following.
  • SA1-1 Examples of amine monomers or acid monomers for introducing such residues into the resin include bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis( 3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, -amino-4-hydroxyphenyl) sulfone, bis[4-(4-aminophenoxy)phenyl]ether, bis(3-amino-4-hydroxyphenyl)ether, 9,9-bis(3-amino-4-hydroxy) phenyl)fluorene, N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)
  • polyimide precursor examples include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide.
  • polyimide examples include resins obtained by dehydrating and ring-closing a polyimide precursor by heating or reaction using a catalyst.
  • polybenzoxazole precursor examples include polyhydroxyamide.
  • polybenzoxazole examples include resins obtained by dehydrating and ring-closing a polybenzoxazole precursor by heating or reaction using a catalyst.
  • polyamide-imide precursor examples include resins obtained by reacting tricarboxylic anhydrides and diamines.
  • polyamide-imide examples include resins obtained by dehydrating and ring-closing a polyamide-imide precursor by heating or reaction using a catalyst.
  • polyamides include resins obtained by reacting dicarboxylic acids or corresponding dicarboxylic acid active diesters with diamines or diisocyanate compounds. Note that the above-mentioned polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor may be a copolymer with polyamide.
  • the polyimide resin may have a structure in which the terminal end of the resin is sealed with a monoamine, a dicarboxylic acid anhydride, or a monocarboxylic acid derivative.
  • the polyimide resin preferably has a crosslinkable group or a radically polymerizable group capable of reacting with the resin at the end of the resin, from the viewpoint of improving adhesion and improving cooling/heating cycle reliability. It is more preferable to have.
  • the binder resin satisfies the following condition (P1a) from the viewpoint of improving adhesion at extremely low temperatures of about -50° C. and improving reliability of cooling and heating cycles. It is more preferable that the binder resin (SA) further satisfies the following condition (P2a).
  • P1a the binder resin
  • P2a the binder resin
  • the binder resin is a polyimide resin, from the same viewpoint, it is also preferable to satisfy the following condition (P1a), and more preferably to satisfy the following condition (P2a).
  • the (SA) binder resin satisfies the following condition (P2a)
  • the following condition (P1a) is satisfied by the fluoride ion in the structure of the (SA) binder resin.
  • P1a) (SA) The content of fluorine elements in the structure of the binder resin is 10,000 mass ppm or less
  • the content of fluoride ions in the structure of the binder resin is 10,000 mass ppm below.
  • the content of the fluorine element in the structure of the binder resin is preferably more than 0.000 mass ppm, more preferably 0.010 mass ppm or more, and 0.030 mass ppm or more. It is more preferably at least 0.050 ppm by mass, even more preferably at least 0.070 ppm by mass, and particularly preferably at least 0.10 ppm by mass.
  • the content of the fluorine element is preferably 10,000 mass ppm or less, more preferably 5,000 mass ppm or less, even more preferably 1,000 mass ppm or less, and 500 mass ppm or less, from the viewpoint of the effects of the invention described above.
  • Fluorine elements have many unshared electron pairs, and it is thought that by including fluorine elements in the structure of the (SA) binder resin, it becomes easier to form coordinate bonds with the surface of the component through electron donation using these electron pairs.
  • the preferable range of the content of fluoride ions in the structure of the binder resin (SA) is also the same as the preferable range of the content of fluorine elements in the structure of the binder resin (SA) with respect to the upper limit and lower limit, respectively. The same is true.
  • the content of the fluorine element in the structure of the binder resin may be 0.000 mass ppm.
  • the content of fluoride ions in the structure of the binder resin may also be 0.000 mass ppm.
  • the content of fluorine element, fluoride ions, or anions containing fluorine element derived from these resins can be reduced. Since the amount is below a specific value, it is presumed that the local interaction with the surfaces of the members to be joined is improved due to the hydrogen bonds of each component in the film, the electronegativity of fluorine atoms, etc.
  • the polarization structure and charge balance in the film can be controlled, and the effects of ionic components that adversely affect the mechanical properties of the film during cooling and heating cycles can be suppressed. it is conceivable that. Due to these effects, it functions as an anchor at the interface with the member at extremely low temperatures, so it is presumed that the followability to each member is improved, and the adhesion and thermal cycle reliability are improved.
  • SA1 Resin is used for (SA1-2) silicone resin and/or polysiloxane (hereinafter referred to as "(SA1-2) Resin ”).
  • the resin for example, one or more types selected from the group consisting of bifunctional organosilane, trifunctional organosilane, tetrafunctional organosilane, and monofunctional organosilane can be hydrolyzed and obtained by dehydration condensation. Examples include resins that can be used. Note that in the resin (SA1-2), a functional group may be introduced into the organic group on the silicon atom by hydrosilylation.
  • a silicone resin is a resin whose main skeleton is a structural unit containing a silicone structure. That is, the main skeleton is a bifunctional organosilane unit having two organic groups on a silicon atom and bonding the silicon atom to two oxygen atoms.
  • the content ratio of bifunctional organosilane units to all organosilane units is 50 mol% or more, preferably 60 mol% or more, and more preferably 70 mol% or more.
  • the content ratio of the bifunctional organosilane unit is preferably 100 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol%.
  • Polysiloxane is a resin whose main skeleton is a structural unit containing a siloxane structure. That is, it has one organic group having two organic groups on a silicon atom, and has a trifunctional organosilane unit as a main skeleton in which the silicon atom is bonded to three oxygen atoms.
  • the content ratio of trifunctional organosilane units to all organosilane units is 50 mol% or more, preferably 60 mol% or more, and more preferably 70 mol% or more.
  • the content ratio of the trifunctional organosilane unit is preferably 100 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol%.
  • the resin preferably has one or more types selected from the group consisting of the following units (3) and (4).
  • Organosilane unit, tetrafunctional organosilane unit, or monofunctional organosilane unit preferably has one or more types selected from the group consisting of the following units (3) and (4).
  • Organosilane unit, tetrafunctional organosilane unit, or monofunctional organosilane unit preferably has one or more types selected
  • the silicone resin preferably has a bifunctional organosilane unit having an aliphatic group and/or a bifunctional organosilane unit having an aromatic group.
  • the polysiloxane preferably has a trifunctional organosilane unit having an aliphatic group and/or a trifunctional organosilane unit having an aromatic group.
  • the aliphatic group contained in the resin is preferably an alkyl group.
  • the number of carbon atoms in the alkyl group is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.
  • the number of carbon atoms in the alkyl group is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • the alkyl group is preferably a methyl group, ethyl group, propyl group, butyl group, or hexyl group.
  • the number of carbon atoms in the aromatic group contained in the resin is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more. On the other hand, the number of carbon atoms in the aromatic group is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less.
  • the aromatic group is preferably a phenyl group, tolyl group, xylyl group, phenoxy group, tolyloxy group, or xylyloxy group.
  • the total content ratio of the above units (3) to all organosilane units is 70 mol from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving cooling and heating cycle reliability. % or more, more preferably 80 mol% or more, even more preferably 85 mol% or more, particularly preferably 90 mol% or more.
  • the total content ratio of the units of (3) in all organosilane units is preferably 100 mol% or less, more preferably 99 mol% or less, and even more preferably 97 mol% or less, from the viewpoint of improving cooling and heating cycle reliability. Particularly preferred is 95 mol% or less.
  • the total content ratio of the units in (4) to all organosilane units is preferably 1.0 mol% or more, and 3.0 mol% or more from the viewpoint of improving cooling/heating cycle reliability. More preferably, it is 5.0 mol% or more.
  • the total content ratio of the above units (4) in all organosilane units is preferably 20 mol% or less, and 15 mol% % or less is more preferable, and even more preferably 10 mol% or less.
  • the resin preferably further has the following unit (5). (5) Bifunctional organosilane unit, trifunctional organosilane unit, tetrafunctional organosilane unit, or monofunctional organosilane unit having an epoxy group (SA1-2)
  • the resin contains a bifunctional organosilane unit having an epoxy group and It is preferable to have a trifunctional organosilane unit having/or an epoxy group.
  • the total content ratio of the above units (5) to all organosilane units is 1.
  • the content is preferably at least .0 mol%, more preferably at least 3.0 mol%, even more preferably at least 5.0 mol%.
  • the total content ratio of the units (5) in all organosilane units is preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less, from the viewpoint of improving cooling/heating cycle reliability.
  • the resin (SA1-2) as described above has a structural unit containing a silicone structure or a siloxane structure as its main skeleton and has excellent flexibility, so the shear strain at -50°C is adjusted within the range of 0.70 to 20, And/or it is suitable for adjusting the elastic modulus at -50°C within the range of 0.10 to 200 MPa.
  • the film of the present invention may contain other (SA) binder resins.
  • Other (SA) binder resins include maleimide resin, maleimide-styrene resin, maleimide-triazine resin, cardo resin, epoxy (meth)acrylate resin, acrylic resin, phenol resin, phenol aralkyl resin, polyhydroxystyrene, and tetrafluoroethylene.
  • Preferred are polyphenylene ether, liquid crystal polymer, cycloolefin polymer, or benzocyclobutene resin.
  • Known resins may be used as these resins.
  • the other (SA) binder resin preferably has an acidic group or a structure derived from an acidic group, and more preferably has an acidic group or a structure derived from an acidic group in the repeating unit of the resin. Examples and preferred descriptions of the acidic group are the same as those of the acidic group contained in the (SA) binder.
  • a maleimide resin is a resin having at least two maleimide groups in at least one of the main chain of the resin, the side chain of the resin, and the end of the resin. Note that maleimide resin is different from polyimide resin.
  • maleimide-styrene resin examples include resins obtained by radical copolymerizing the above maleimide resin with a styrene derivative. Also included are resins obtained by radical copolymerization of maleimide compounds and styrene derivatives with other copolymerization components such as (meth)acrylic acid derivatives.
  • maleimide-triazine resins examples include resins obtained by further reacting the above maleimide resin with a compound having a triazine structure and/or an aromatic cyanate ester compound. Also included are resins obtained by reacting a maleimide compound with a compound having a triazine structure and/or an aromatic cyanate ester compound.
  • maleimide-oxazine resins examples include resins obtained by reacting the above maleimide resin with a compound having a benzoxazine structure. Also included are resins obtained by reacting a maleimide compound with a compound having a benzoxazine structure.
  • the total content ratio of the (SA1) resin to the total 100 mass% of the (SA) binder resin is 50 mass% or more from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving cooling/heating cycle reliability. It is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. On the other hand, from the viewpoint of improving adhesion, the total content ratio of the (SA1) resin is preferably 100% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.
  • the total content ratio of the (SA) binder resin in the film is preferably 10% by volume or more, more preferably 15% by volume or more, and even more preferably 20% by volume or more.
  • the total content ratio of the (SA) binder resin in the film is preferably 50% by volume or less, more preferably 40% by volume or less, and even more preferably 30% by volume or less.
  • the film of the present invention preferably contains an (SB) epoxy compound or a compound having a structure derived from an epoxy compound (hereinafter referred to as "(SB) compound").
  • the (SB) compound may be an epoxy compound or a compound having a structure derived from an epoxy compound.
  • the epoxy compound may be a compound in the composition for forming the film of the present invention.
  • the (SB) compound is preferably a compound that forms or has formed a crosslinked structure with the (SA) binder resin.
  • the number of epoxy groups contained in the (SB) compound is preferably 2 or more, and more preferably 3 or more. On the other hand, the number of the above epoxy groups is preferably 6 or less, and more preferably 4.
  • the film of the present invention contains a (SB) compound from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving cooling and heating cycle reliability, (SB1) A compound having a structure containing an oxyalkylene group (hereinafter referred to as "(SB1) compound”), (SB2) A compound having a structure containing at least two aromatic structures, and an oxyalkylene group (hereinafter referred to as "(SB2) compound”), and (SB3) a compound having a tertiary amine structure bonded to an arylene group and two divalent organic groups (hereinafter referred to as "(SB3) compound").
  • SB1 A compound having a structure containing an oxyalkylene group
  • (SB2) compound having a structure containing at least two aromatic structures, and an oxyalkylene group hereinafter referred to as "(SB2) compound
  • (SB3) a compound having a tertiary amine structure bonded to an arylene group and
  • the (SB1) compound, (SB2) compound, and (SB3) compound may be compounds having structures derived from the respective above-mentioned compounds. Note that the compound (SB1) is a compound different from the compound (SB2) and does not have a structure containing an aromatic structure.
  • the oxyalkylene group that the compound (SB1) has is preferably divalent or higher, more preferably trivalent or higher.
  • the oxyalkylene group contained in the compound (SB1) preferably has a valence of 6 or less, and more preferably a valence of 4 or less.
  • the number of oxyalkylene groups that the compound (SB1) has is preferably 1 or more, more preferably 4 or more, even more preferably 6 or more, and particularly preferably 10 or more. On the other hand, the number of the above oxyalkylene groups is preferably 20 or less, more preferably 17 or less, and even more preferably 15 or less.
  • the number of carbon atoms in the oxyalkylene group of the compound (SB1) is preferably 1 or more, more preferably 2 or more. On the other hand, the number of carbon atoms in the oxyalkylene group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the compound (SB1) preferably contains one or more types selected from the group consisting of a compound represented by general formula (21) and a compound having a structure represented by general formula (22).
  • X 5 represents an alkylene group having 1 to 30 carbon atoms.
  • m represents an integer from 1 to 20.
  • * 1 to * 4 each independently represent a bonding point with another structure.
  • the alkylene group having 1 to 30 carbon atoms is preferably a methylene group, ethylene group, propylene group, butylene group, or hexylene group. Note that the alkylene group has a linear structure or a branched structure. The above alkylene group may have a hetero atom and may be unsubstituted or substituted.
  • the structure containing at least two aromatic structures possessed by the (SB2) compound is preferably bonded to at least two oxyalkylene groups, and is preferably a divalent or higher structure via these at least two oxyalkylene groups.
  • the above divalent or higher structure is more preferably trivalent or higher.
  • the above divalent or higher structure is preferably hexavalent or lower, more preferably tetravalent or lower.
  • the number of carbon atoms in the aromatic structure of the compound (SB2) is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more. On the other hand, the number of carbon atoms in the aromatic structure is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less.
  • the number of aromatic structures that the compound (SB2) has is preferably 2 or more, more preferably 3 or more. On the other hand, the number of the above aromatic structures is preferably 6 or less, more preferably 4 or less.
  • the structure containing at least two aromatic structures in the compound preferably has a group that connects the at least two aromatic structures.
  • the above connecting groups include a direct bond, an alkylene group having 1 to 6 carbon atoms, a halogenated alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, an arylene group having 6 to 15 carbon atoms, a carbon Preferred are 6 to 15 oxyaryleneoxy groups, ether bonds, carbonyl groups, carboxylic ester bonds, amide bonds, urea bonds, urethane bonds, sulfonyl groups, or carbonate ester bonds.
  • the number of oxyalkylene groups that the compound (SB2) has is preferably 2 or more, more preferably 4 or more, even more preferably 6 or more, and particularly preferably 10 or more.
  • the number of the above oxyalkylene groups is preferably 20 or less, more preferably 17 or less, and even more preferably 15 or less.
  • the number of carbon atoms in the oxyalkylene group of the compound (SB2) is preferably 1 or more, more preferably 2 or more.
  • the number of carbon atoms in the oxyalkylene group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the (SB2) compound preferably includes one or more compounds selected from the group consisting of compounds represented by general formula (23) and compounds having a structure represented by general formula (24).
  • X 6 and X 7 each independently represent an alkylene group having 1 to 30 carbon atoms.
  • Y 6 is a direct bond, an alkylene group having 1 to 6 carbon atoms, a halogenated alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, an arylene group having 6 to 15 carbon atoms, or an arylene group having 6 to 6 carbon atoms.
  • 15 oxyaryleneoxy groups, ether bonds, carbonyl groups, carboxylic ester bonds, amide bonds, urea bonds, urethane bonds, sulfonyl groups, or carbonate ester bonds are preferable.
  • R 33 and R 34 each independently represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxy group.
  • the rings connected by a ring-forming group represent a monocyclic or fused polycyclic hydrocarbon ring.
  • a and b each independently represent an integer of 0 to 4.
  • m and n each independently represent an integer of 1 to 20.
  • * 1 to * 4 each independently represent a bonding point with another structure.
  • the alkyl group having 1 to 6 carbon atoms is preferably a methyl group, an ethyl group, or a propyl group.
  • the cycloalkyl group having 4 to 7 carbon atoms is preferably a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.
  • the aryl group having 6 to 15 carbon atoms is preferably a phenyl group, tolyl group, or xylyl group.
  • the alkoxy group having 1 to 6 carbon atoms is preferably a methoxy group, an ethoxy group, or a propoxy group.
  • the alkylene group having 1 to 30 carbon atoms is preferably a methylene group, ethylene group, propylene group, butylene group, or hexylene group.
  • the alkylene group having 1 to 6 carbon atoms is preferably a methylene group, an ethylene group, or a propylene group.
  • the cycloalkylene group having 4 to 7 carbon atoms is preferably a cyclobutylene group, a cyclopentylene group, or a cyclohexylene group. Note that the alkyl group and alkylene group have a linear structure or a branched structure.
  • the above alkyl group, cycloalkyl group, aryl group, alkoxy group, alkylene group, and cycloalkylene group may have a heteroatom and may be unsubstituted or substituted.
  • the tertiary amine structure of the (SB3) compound is bonded to an arylene group and two divalent organic groups, and is preferably a trivalent or higher structure mediated by these arylene groups and two divalent organic groups.
  • the trivalent or higher structure is preferably hexavalent or lower, and more preferably tetravalent or lower.
  • the number of carbon atoms in the arylene group of the compound (SB3) is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more. On the other hand, the number of carbon atoms in the above arylene group is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less.
  • the number of aromatic rings in the arylene group of the compound (SB3) is preferably one or more, more preferably two or more. On the other hand, the number of aromatic rings is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the compound (SB3) has an oxyalkylene group.
  • the arylene group in the compound (SB3) is preferably an arylene group bonded to an oxyalkylene group.
  • the divalent organic group in the compound (SB3) is preferably a divalent aliphatic group, and more preferably an alkylene group.
  • the divalent aliphatic group in the compound (SB3) is preferably a divalent aliphatic group bonded to the oxyalkylene group.
  • the number of oxyalkylene groups that the compound (SB3) has is preferably 2 or more, more preferably 4 or more, even more preferably 6 or more, and particularly preferably 10 or more.
  • the number of the above oxyalkylene groups is preferably 20 or less, more preferably 17 or less, and even more preferably 15 or less.
  • the number of carbon atoms in the oxyalkylene group of the compound (SB3) is preferably 1 or more, more preferably 2 or more.
  • the number of carbon atoms in the oxyalkylene group is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the compound preferably contains one or more types selected from the group consisting of a compound represented by general formula (25) and a compound having a structure represented by general formula (26).
  • X 8 , X 9 and X 10 each independently represent an alkylene group having 1 to 30 carbon atoms.
  • R 35 is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, or a group forming a ring. represents.
  • the rings connected by a ring-forming group represent a monocyclic or fused polycyclic hydrocarbon ring.
  • a represents an integer from 0 to 4.
  • l, m, and n each independently represent an integer of 0 to 20.
  • * 1 to * 6 each independently represent a bonding point with another structure.
  • the alkyl group having 1 to 6 carbon atoms is preferably a methyl group, an ethyl group, or a propyl group.
  • the cycloalkyl group having 4 to 7 carbon atoms is preferably a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.
  • the aryl group having 6 to 15 carbon atoms is preferably a phenyl group, tolyl group, or xylyl group.
  • the alkoxy group having 1 to 6 carbon atoms is preferably a methoxy group, an ethoxy group, or a propoxy group.
  • the alkylene group having 1 to 30 carbon atoms is preferably a methylene group, ethylene group, propylene group, butylene group, or hexylene group. Note that the alkyl group and alkylene group have a linear structure or a branched structure.
  • the above alkyl group, cycloalkyl group, aryl group, alkoxy group, and alkylene group may have a heteroatom and may be unsubstituted or substituted.
  • the above compounds (SB1), (SB2), and (SB3) have flexible skeletons derived from oxyalkylene groups that adjust the shear strain at -50°C within the range of 0.70 to 20, and/ Alternatively, it is suitable for adjusting the elastic modulus at -50°C within the range of 0.10 to 200 MPa. Furthermore, the (SB) compound is thought to function as an anchor at the interface with the members at extremely low temperatures due to its ability to coordinate with each member derived from the tertiary amine structure. Therefore, it is estimated that the followability to each member is improved, and the adhesion and cooling/heating cycle reliability are improved.
  • the total content of the (SB1) compound, (SB2), and (SB3) compound in the film is preferably 0.10 parts by mass or more, and 0.50 parts by mass, based on 100 parts by mass of the (SA) binder resin. It is more preferably at least 1.0 parts by mass, even more preferably at least 3.0 parts by mass, and particularly preferably at least 5.0 parts by mass.
  • the total content of the (SB1) compound, (SB2), and (SB3) compound in the film is preferably 20 parts by mass or less, more preferably 15 parts by mass or less.
  • the film of the present invention preferably contains an (SC) amine compound or a compound having a structure derived from an amine compound (hereinafter referred to as "(SC) compound").
  • the (SC) compound may be an amine compound or a compound having a structure derived from an amine compound.
  • the amine compound may be a compound in the composition for forming the film of the present invention.
  • the (SC) compound is preferably a compound that forms or has formed a crosslinked structure with the above (SB) compound.
  • the crosslinked structure is preferably formed by reaction, and is not particularly limited, and may be formed by heating, irradiation with energy rays, etc.
  • the number of amino groups that the (SC) compound has is preferably 2 or more, more preferably 3 or more. On the other hand, the number of the above amino groups is preferably 6 or less, more preferably 4.
  • the film of the present invention contains a (SC) compound from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability,
  • SC1 A compound having a silicone structure and/or siloxane structure and at least two alkylene groups bonded to silicon atoms in the silicone structure and/or siloxane structure (hereinafter referred to as "(SC1) ) compound").
  • SC1 The compound may be a compound having a structure derived from the above compound.
  • the silicone structure and siloxane structure of the compound (SC1) are bonded to at least two alkylene groups, and are preferably divalent or higher-valent structures via these alkylene groups.
  • the above bivalent or higher valence structure is more preferably trivalent or higher.
  • the above-mentioned structure having a valence of 2 or more is preferably 6 or less, more preferably 4 or less.
  • the number of silicon atoms in the (SC1) compound is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, and particularly preferably 20 or more.
  • the number of silicon atoms contained in the compound (SC1) is preferably 30 or less, more preferably 27 or less, and even more preferably 25 or less.
  • the silicone structure in the compound (SC1) is preferably a dialkyl silicone structure and/or a monoalkyl silicone structure.
  • the number of carbon atoms in the alkyl group that the dialkyl silicone structure and monoalkyl silicone structure have is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.
  • the number of carbon atoms in the alkyl group is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • the siloxane structure in the compound (SC1) is preferably a monoalkylsiloxane structure.
  • the number of carbon atoms in the alkyl group of the monoalkylsiloxane structure is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.
  • the number of carbon atoms in the alkyl group is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • the content ratio of the aliphatic group to the total of the aliphatic group and aromatic group bonded to the silicon atom in the silicone structure and the siloxane structure in the compound is preferably 80 mol% or more, and 85 mol% or more. More preferably, 90 mol% or more is even more preferable.
  • the content ratio of the aliphatic group to the total of the aliphatic group and aromatic group is preferably 100 mol% or less, more preferably 99 mol% or less, and 97 mol% or less from the viewpoint of improving the reliability of the cooling/heating cycle. is even more preferable.
  • the aliphatic group that the compound (SC1) has is preferably an alkyl group.
  • the preferred number of carbon atoms in the alkyl group is also the same as above.
  • the alkyl group is preferably a methyl group, ethyl group, propyl group, butyl group, or hexyl group.
  • the number of carbon atoms in the aromatic group that the compound (SC1) has is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more.
  • the number of carbon atoms in the aromatic group is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less.
  • the aromatic group is preferably a phenyl group, tolyl group, xylyl group, phenoxy group, tolyloxy group, or xylyloxy group.
  • the compound (SC1) preferably contains one or more types selected from the group consisting of a compound represented by general formula (31) and a compound having a structure represented by general formula (32).
  • X 11 and X 12 are each independently a direct bond, an oxygen atom, an alkylene group having 1 to 30 carbon atoms, an alkyleneoxy group having 1 to 30 carbon atoms, Or represents an arylene group having 6 to 30 carbon atoms.
  • R 41 to R 46 each independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms.
  • x represents an integer from 1 to 100.
  • * 1 to * 4 each independently represent a bonding point with another structure.
  • the alkyl group having 1 to 30 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group.
  • the aryl group having 6 to 30 carbon atoms is preferably a phenyl group, a tolyl group, or a xylyl group.
  • the aryloxy group having 6 to 30 carbon atoms is preferably a phenoxy group, a tolyloxy group, or a xylyloxy group.
  • the alkylene group having 1 to 30 carbon atoms is preferably a methylene group, an ethylene group, a propylene group, a butylene group, or a hexylene group.
  • the arylene group having 6 to 30 carbon atoms is preferably a phenylene group, a tolylene group, or a xylylene group.
  • the alkyl group and the alkylene group have a linear structure or a branched structure.
  • the above alkyl group, aryl group, aryloxy group, alkylene group, and arylene group may have a heteroatom and may be either unsubstituted or substituted.
  • the above-mentioned (SC1) compound has a flexible skeleton derived from a silicone structure and/or a siloxane structure, and has a shear strain at -50°C adjusted to within a range of 0.70 to 20, and/or a shear strain at -50°C. It is suitable for adjusting the elastic modulus within the range of 0.10 to 200 MPa.
  • the content of the (SC1) compound in the film is preferably 1.0 part by mass or more, more preferably 3.0 parts by mass or more, even more preferably 5.0 parts by mass or more, and particularly preferably 6.0 parts by mass or more, when the total of the (SA) binder resin, the (SB) compound, and the (SC) compound is 100 parts by mass.
  • the content of the (SC1) compound in the film is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less.
  • the film of the present invention contains (SD) thermally conductive filler.
  • SD Thermal conductive filler refers to inorganic particles having a thermal conductivity of 2.0 W/(m ⁇ K) or more at 25°C. The thermal conductivity can be determined by obtaining a sintered body having a thickness of around 1.0 mm and a porosity of 10% by volume or less, and then measuring it according to "JIS R1611 (2010)".
  • the shape of the thermally conductive filler includes, for example, true spherical shape, spherical shape, scale shape, flake shape, foil shape, fiber shape, or needle shape. From the viewpoint of improving the thermal conductivity of the film due to high-density filling of the filler, a true spherical (SD) thermally conductive filler is preferable.
  • the thermal conductivity of the thermally conductive filler at 25°C is preferably 2.0 W/(m ⁇ K) or more, and 5.0 W/(m ⁇ K) from the viewpoint of improving adhesion and improving cooling/heating cycle reliability. ) or more is more preferable, 10W/(m ⁇ K) or more is even more preferable, 20W/(m ⁇ K) or more is even more preferable, 30W/(m ⁇ K) or more is particularly preferable, 40W/(m ⁇ K) or more is particularly preferred.
  • the thermal conductivity of the (SD) thermally conductive filler at 25°C is preferably 300 W/(m ⁇ K) or less, more preferably 200 W/(m ⁇ K) or less, and 150 W /(m ⁇ K) or less is more preferable, and 100 W/(m ⁇ K) or less is particularly preferable.
  • the thermally conductive filler preferably contains aluminum, boron, silicon, magnesium, zinc, titanium, zirconium, yttrium, or iron as a main component from the viewpoint of improving adhesion and improving cooling/heating cycle reliability. , aluminum, boron, silicon, magnesium, or zinc as the main component elements. Note that the main component element refers to the element that is contained in the largest amount based on mass among the constituent components.
  • Thermal conductive fillers include alumina particles, aluminum nitride particles, boron nitride particles, silica particles, silicon carbide particles, silicon nitride particles, magnesium oxide particles, magnesium carbonate particles, magnesium hydroxide particles, zinc oxide particles, and titanium carbide. It is preferable that the particles include at least one type selected from the group consisting of particles, titanium nitride particles, titanium oxide particles, zirconium oxide particles, yttrium oxide particles, and iron oxide particles.
  • the (SD) thermally conductive filler described above maintains the mechanical properties of the film and increases the thermal conductivity of the film at 25°C from 0.10 to 5.0 W/( It is suitable for adjustment within the range of m ⁇ K).
  • the thermally conductive filler includes (SD1) a first thermally conductive filler and (SD2) a second thermally conductive filler, (SD1)
  • the average primary particle diameter of the first thermally conductive filler is 1.0 to 200 ⁇ m
  • SD2 The average primary particle diameter of the second thermally conductive filler is 0.010 ⁇ m or more and less than 1.0 ⁇ m.
  • the thermally conductive filler is the first thermally conductive filler (SD1) and the second thermally conductive filler (SD2) from the viewpoint of improving adhesion and improving the reliability of cooling and heating cycles.
  • it contains a thermally conductive filler, (SD1)
  • the average primary particle diameter of the first thermally conductive filler is 1.0 to 200 ⁇ m
  • SD2 It is more preferable that the average primary particle diameter of the second thermally conductive filler is 0.010 ⁇ m or more and less than 1.0 ⁇ m.
  • the average primary particle diameter of the first thermally conductive filler is preferably 2.0 ⁇ m or more, more preferably 3.0 ⁇ m or more, from the viewpoint of high-density filling of the filler and clarification of the filler interface.
  • the gaps between the larger particle size fillers are filled with smaller particle size fillers, which significantly improves the thermal conductivity of the film due to the high density of the fillers.
  • efficient heat dissipation reduces internal stress caused by temperature increases in the components, and the film is believed to have better adhesion and thermal cycle reliability due to improved conformity to each component.
  • the average primary particle diameter of the first thermally conductive filler is preferably 5.0 ⁇ m or more, more preferably 10 ⁇ m or more, even more preferably 15 ⁇ m or more, even more preferably 20 ⁇ m or more, from the viewpoint of improving cooling and heating cycle reliability.
  • the thickness is particularly preferably 25 ⁇ m or more, particularly preferably 30 ⁇ m or more.
  • the average primary particle diameter is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 80 ⁇ m or less.
  • the thickness is preferably 60 ⁇ m or less, more preferably 50 ⁇ m or less, even more preferably 45 ⁇ m or less, and particularly preferably 40 ⁇ m or less.
  • the average primary particle diameter of the second thermally conductive filler is preferably 0.050 ⁇ m or more, more preferably 0.10 ⁇ m or more, even more preferably 0.15 ⁇ m or more, from the viewpoint of improving cooling/heating cycle reliability. Particularly preferred is 20 ⁇ m or more. On the other hand, from the viewpoint of improving adhesion, the average primary particle diameter is preferably 0.80 ⁇ m or less, more preferably 0.60 ⁇ m or less, and even more preferably 0.40 ⁇ m or less.
  • the primary particle diameter of the thermally conductive filler refers to the major axis diameter of the primary particles of the filler.
  • the average primary particle diameter of the (SD) thermally conductive filler in the film is the average of 30 filler primary particles measured by imaging and analyzing the cross section of the film using a transmission electron microscope (hereinafter referred to as "TEM"). It can be calculated as a value.
  • TEM transmission electron microscope
  • the average primary particle diameter of the first thermally conductive filler is the average value obtained by measuring 30 filler primary particles having a primary particle diameter of 1.0 ⁇ m or more in measurement using a TEM.
  • the average primary particle diameter of the second thermally conductive filler is the average value obtained by measuring 30 filler primary particles having a primary particle diameter of less than 1.0 ⁇ m in a measurement using a TEM.
  • the elements contained in the thermally conductive filler can be detected by imaging and analyzing a cross section of the film using a transmission electron microscope-energy dispersive X-ray spectroscopy (hereinafter referred to as "TEM-EDX"). Measurement using TEM-EDX makes it possible to distinguish between two or more types of fillers and to clarify filler interfaces.
  • the average primary particle diameter of the thermally conductive filler in the filler dispersion is determined by measuring the particle size distribution using a laser diffraction/scattering method. Examples of the measuring device include SLD3100 manufactured by Shimadzu Corporation, LA-920 manufactured by Horiba Corporation, or equivalent products thereof.
  • the specific surface area of the first thermally conductive filler is preferably 0.023 m 2 /g or more, more preferably 0.031 m 2 /g or more, and 0.047 m 2 /g or more. It is more preferable, and 0.059 m 2 /g or more is particularly preferable. Further, from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving cooling/heating cycle reliability, it is preferably 0.080 m 2 /g or more, more preferably 0.11 m 2 /g or more, and 0.15 m 2 /g.
  • it is preferably 0.18 m 2 /g or more, more preferably 0.20 m 2 /g or more, and even more preferably 0.23 m 2 /g or more.
  • the specific surface area of the first thermally conductive filler is preferably 5.90 m 2 /g or less, and 3.00 m 2 /g or less from the viewpoint of high-density filling of the filler and clarification of the filler interface. More preferably, it is 2.00 m 2 /g or less. Furthermore, from the viewpoint of improving cooling and heating cycle reliability, the area is preferably 1.20 m 2 /g or less, more preferably 1.00 m 2 /g or less, even more preferably 0.80 m 2 /g or less, and 0.60 m 2 /g or less. is more preferable, 0.50 m 2 /g or less is particularly preferable, and 0.40 m 2 /g or less is particularly preferable.
  • it is preferably 2.00 m 2 /g or less, more preferably 1.20 m 2 /g or less, even more preferably 1.00 m 2 /g or less, and 0. It is more preferably .80 m 2 /g or less, even more preferably 0.60 m 2 /g or less, even more preferably 0.50 m 2 /g or less, and particularly preferably 0.40 m 2 /g or less.
  • the above-mentioned configuration reduces the slope of the stress-strain curve, with stress on the vertical axis and strain on the horizontal axis, due to the anchor effect of the filler with a specific specific surface area (the strain per unit stress increases), making it ideal for adjusting the shear strain at -50°C to within the range of 0.70 to 20.
  • it has flexibility that can mitigate the difference in thermal expansion coefficient between components even at extremely low temperatures, and it is estimated that the adhesion and heat cycle reliability will be improved because the material has improved conformity to each component.
  • the specific surface area of the second thermally conductive filler is preferably 5.91 m 2 /g or more, more preferably 8.00 m 2 /g or more, and 12.0 m 2 /g or more. It is more preferably 14.6 m 2 /g or more, particularly preferably 16.1 m 2 /g or more, and particularly preferably 19.5 m 2 /g or more.
  • the specific surface area of the second thermally conductive filler is preferably 590 m 2 /g or less, more preferably 120 m 2 /g or less, and 60.0 m 2 /g or less from the viewpoint of improving cooling and heating cycle reliability. It is more preferably 50.0 m 2 /g or less, even more preferably 40.0 m 2 /g or less, particularly preferably 30.0 m 2 /g or less.
  • the voids between fillers with large particle sizes are filled with fillers with small particle sizes, so the heat generated in the parts to be joined can be efficiently radiated, and the heat generated by the parts to be joined can be dissipated efficiently. It is thought that the internal stress caused by this process can be reduced. In addition, it is also presumed that the heat stored in the film can be reduced, and changes in mechanical properties due to temperature increases in the film can be suppressed.
  • the specific surface area of the (SD) thermally conductive filler can be calculated by measuring the BET specific surface area by the gas adsorption method. First, the film is heated at 600 to 900°C to thermally decompose and/or volatilize organic components such as resin, and the mass of the remaining (SD) thermally conductive filler is measured. Next, gas molecules are adsorbed and the BET specific surface area is calculated from the monomolecular adsorption amount. The remaining (SD) thermally conductive filler can be imaged and analyzed using a TEM to measure the primary particle diameter of the filler, thereby determining whether it corresponds to the first thermally conductive filler (SD1) or the second thermally conductive filler (SD2).
  • the remaining (SD) thermally conductive filler is a mixture of the first thermally conductive filler (SD1) and the second thermally conductive filler (SD2)
  • the specific surface area of each can be measured by separating the two types of filler using a dry classifier or a wet classifier.
  • the content ratio of the (SD1) first thermally conductive filler and (SD2) the second thermally conductive filler is determined from the viewpoint of improving adhesion and improving cooling/heating cycle reliability.
  • the total is 100% by volume, it is preferably 40% by volume or more, more preferably 50% by volume or more, and even more preferably 60% by volume or more.
  • the content ratio of the first thermally conductive filler (SD1) is preferably 80 volume% or less, more preferably 75 volume% or less, and 70 volume% or less from the viewpoint of improving adhesion and improving cooling/heating cycle reliability. More preferred.
  • the content ratio of the second thermally conductive filler is determined from the viewpoint of improving adhesion and improving cooling/heating cycle reliability.
  • the total is 100% by volume, it is preferably 20% by volume or more, more preferably 25% by volume or more, and even more preferably 30% by volume or more.
  • the content ratio of the first thermally conductive filler (SD1) is preferably 60 volume% or less, more preferably 50 volume% or less, and 40 volume% or less from the viewpoint of improving adhesion and improving cooling/heating cycle reliability. More preferred.
  • the film of the present invention may contain other (SD) thermally conductive fillers.
  • Other (SD) thermally conductive fillers include, for example, carbon black or metal fillers such as aluminum particles, magnesium particles, silver particles, zinc particles, iron particles, or lead particles.
  • the content ratio of the (SD) thermally conductive filler in the film is preferably 50 volume% or more, more preferably 60 volume% or more, and even more preferably 70 volume% or more.
  • the content ratio of the (SD) thermally conductive filler in the film is preferably 90% by volume or less, more preferably 85% by volume or less, and even more preferably 80% by volume or less.
  • the content rate of the thermally conductive filler can be calculated using a method measured by thermogravimetric analysis or an equivalent method. First, the film is heated at 600 to 900°C to thermally decompose and/or volatilize organic components such as resin, the mass of the remaining (SD) thermally conductive filler is measured, and from the difference, the amount of organic components such as resin is determined. Calculate the mass. Next, a method of calculating the volumes of organic components such as (SD) thermally conductive filler and resin by dividing the obtained mass by their respective specific gravity can be mentioned.
  • the film of the present invention has the following (S1a), (S2a), (S3a), (S1b), (S2b), It is preferable that at least one of the conditions (S3b) and (S3b) is satisfied. From the same viewpoint, the film of the present invention more preferably satisfies at least one of the following conditions (S1a), (S2a), and (S3a), and the following (S1a), (S2a), and ( It is more preferable that at least one of the conditions in S3a) is satisfied and at least one of the following conditions in (S1b), (S2b), and (S3b) is satisfied.
  • the film of the present invention satisfies the following condition (S3b), the following condition (S3a) is satisfied by the chloride ions and bromide ions in the film.
  • S1a The content of boron element in the film is 5.0% by mass or less
  • S2a The content of phosphorus element in the film is 1,000 mass ppm or less
  • S3a The content of chlorine element and bromine element in the film
  • the total content of ions containing boron element in the film is 5.0 mass % or less
  • S2b The total content of ions containing phosphorus element in the film is 5.0 mass % or less
  • S1b ,000 mass ppm or less
  • S3b The total content of chloride ions and bromide ions in the film is 1,000 mass ppm or less.
  • the film of the present invention preferably contains the following (I) and/or (II).
  • the content of boron element in the film is preferably 0.010% by mass or more, more preferably 0.030% by mass or more, even more preferably 0.050% by mass or more, even more preferably 0.070% by mass or more, and 0.030% by mass or more. .10% by mass or more is particularly preferred.
  • the content of boron element in the film is preferably 4.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, particularly preferably 1.0% by mass or less. .
  • the content of elemental phosphorus in the film is preferably 0.010 mass ppm or more, more preferably 0.030 mass ppm or more, even more preferably 0.050 mass ppm or more, even more preferably 0.070 mass ppm or more, and 0.050 mass ppm or more. .10 mass ppm or more is particularly preferred.
  • the content of the phosphorus element in the film is preferably 500 mass ppm or less, more preferably 300 mass ppm or less, even more preferably 100 mass ppm or less, even more preferably 50 mass ppm or less, and even more preferably 30 mass ppm or less. , more preferably 10 mass ppm or less, further preferably 5.0 mass ppm or less, particularly preferably 3.0 mass ppm or less, particularly preferably 1.0 mass ppm or less.
  • the preferred range of the total content of chlorine element and bromine element in the film is also the same as the above-mentioned phosphorus element content for each of the upper limit and lower limit.
  • the total content of ions containing boron elements in the film is preferably 0.010% by mass or more, more preferably 0.030% by mass or more, even more preferably 0.050% by mass or more, and 0.070% by mass or more. is more preferable, and 0.10% by mass or more is particularly preferable.
  • the total content of ions containing boron element in the film is preferably 4.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, and 1.0% by mass or less. % or less is particularly preferable.
  • the total content of ions containing the phosphorus element in the film is preferably 0.010 mass ppm or more, more preferably 0.030 mass ppm or more, even more preferably 0.050 mass ppm or more, and 0.070 mass ppm or more. is more preferable, and 0.10 mass ppm or more is particularly preferable.
  • the total content of ions containing phosphorus elements in the film is preferably 3,000 mass ppm or less, more preferably 1,000 mass ppm or less, even more preferably 500 mass ppm or less, and still more preferably 300 mass ppm or less. It is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, even more preferably 30 mass ppm or less, particularly preferably 10 mass ppm or less, and particularly preferably 5.0 mass ppm or less.
  • the total content of chloride ions and bromide ions in the film is preferably 0.010 mass ppm or more, more preferably 0.030 mass ppm or more, even more preferably 0.050 mass ppm or more, and 0.070 mass ppm.
  • the above is more preferable, and 0.100 mass ppm or more is particularly preferable.
  • the total content of chloride ions and bromide ions in the film is preferably 500 mass ppm or less, more preferably 300 mass ppm or less, even more preferably 100 mass ppm or less, even more preferably 50 mass ppm or less, and 30 mass ppm or less. It is more preferably at most 10 mass ppm, even more preferably at most 5.0 mass ppm, particularly preferably at most 3.0 mass ppm, particularly preferably at most 1.0 mass ppm.
  • the boron element, phosphorus element, chlorine element, or bromine element interacts with the surface of the member to be joined.
  • the boron element has an empty 3p orbital, and it is thought that it is easy to form a coordinate bond from the surface of the member by accepting electrons using this empty orbital.
  • the phosphorus element has a lone pair of electrons, and it is thought that it is easy to form a coordinate bond to the surface of the member by efficiently donating electrons using the 3d orbital, which is an empty atomic orbital.
  • the chlorine element and the bromine element have many unshared electron pairs, and it is thought that by donating electrons using these electron pairs, it is easy to form a coordinate bond with the surface of the member. Due to these effects, it functions as an anchor at the interface with members at extremely low temperatures, so it is presumed that followability to each member is improved, and adhesion and cooling/heating cycle reliability are improved.
  • the film of the present invention preferably satisfies at least one of the following conditions (S3 ⁇ ) and (S3 ⁇ ) from the viewpoint of improving adhesion at extremely low temperatures of about ⁇ 50° C. and improving cooling/heating cycle reliability. From the same viewpoint, the film of the present invention more preferably satisfies the following conditions (S3 ⁇ ), and even more preferably satisfies the following conditions (S3 ⁇ ) and also satisfies the following conditions (S3 ⁇ ). In addition, when the film of the present invention satisfies the following condition (S3 ⁇ ), the following condition (S3 ⁇ ) is satisfied by the fluoride ions in the film. (S3 ⁇ ) The content of fluorine elements in the film is 1,000 mass ppm or less (S3 ⁇ ) The content of fluoride ions in the film is 1,000 mass ppm or less.
  • the film of the present invention preferably contains the following (III) and/or (IV).
  • the content of fluorine element in the film is preferably more than 0.000 mass ppm, more preferably 0.010 mass ppm or more, even more preferably 0.030 mass ppm or more, and still more preferably 0.050 mass ppm or more. It is more preferably 0.070 mass ppm or more, particularly preferably 0.10 mass ppm or more.
  • the content of the fluorine element in the film is preferably 500 mass ppm or less, more preferably 300 mass ppm or less, even more preferably 100 mass ppm or less, even more preferably 50 mass ppm or less, and even more preferably 30 mass ppm or less. , more preferably 10 mass ppm or less, further preferably 5.0 mass ppm or less, particularly preferably 3.0 mass ppm or less, particularly preferably 1.0 mass ppm or less.
  • the content of fluoride ions in the film is preferably more than 0.000 mass ppm, more preferably 0.010 mass ppm or more, even more preferably 0.030 mass ppm or more, and even more preferably 0.050 mass ppm or more. It is more preferably 0.070 mass ppm or more, particularly preferably 0.10 mass ppm or more.
  • the content of fluoride ions in the film is preferably 500 mass ppm or less, more preferably 300 mass ppm or less, even more preferably 100 mass ppm or less, even more preferably 50 mass ppm or less, and still more preferably 30 mass ppm or less. It is preferably 10 mass ppm or less, more preferably 5.0 mass ppm or less, particularly preferably 3.0 mass ppm or less, and particularly preferably 1.0 mass ppm or less.
  • Fluorine element has many unshared electron pairs, and by including fluorine element in the film, it is thought that it is easier to form coordinate bonds with the surface of the component by donating electrons using these electron pairs. .
  • the content of elemental fluorine in the film may be 0.000 ppm by mass.
  • the content of fluoride ions in the film may also be 0.000 ppm by mass.
  • the film of the present invention has a binder resin (SA) or a thermally conductive filler (SD) that has a fluorine atom or a fluoride ion in its structure, or further contains a component containing elemental fluorine and/or a component containing fluoride ions.
  • SA binder resin
  • SD thermally conductive filler
  • the film of the present invention contains a (SB) compound or a (SC) compound, and the content of elemental fluorine and/or the content of fluoride ions in the film exceeds 0.000 mass ppm
  • the film of the present invention includes a component in which (SA) binder resin, (SD) thermally conductive filler, (SB) compound, or (SC) compound has a fluorine atom or fluoride ion in its structure, or further contains a fluorine element.
  • SA binder resin
  • SD thermally conductive filler
  • SB thermally conductive filler
  • SC a fluorine atom or fluoride ion in its structure, or further contains a fluorine element.
  • the fluorine elements and fluoride ions in these components, or the fluorine derived from these components can be reduced. Since the content of anions containing elements is below a specific value, it is assumed that local interaction with the surface of the parts to be joined will improve due to hydrogen bonds of each component in the film, electronegativity of fluorine atoms, etc. Ru.
  • the polarization structure and charge balance in the film can be controlled, and the effects of ionic components that adversely affect the mechanical properties of the film during cooling and heating cycles can be suppressed. it is conceivable that. Due to these effects, it functions as an anchor at the interface with the member at extremely low temperatures, so it is presumed that the followability to each member is improved, and the adhesion and thermal cycle reliability are improved.
  • the film of the present invention preferably satisfies at least one of the following conditions (S4a) and (S4b) from the viewpoint of improving adhesion at extremely low temperatures of about -50° C. and improving cooling/heating cycle reliability. From the same viewpoint, the film of the present invention more preferably satisfies the following condition (S4a), and even more preferably satisfies the following condition (S4a) and also satisfies the following condition (S4b). In addition, when the film of the present invention satisfies the following condition (S4b), the following condition (S4a) is satisfied by the ion containing the platinum element in the film. (S4a) The content of platinum element in the film is 1,000 mass ppm or less (S4b) The total content of ions containing platinum element in the film is 5,000 mass ppm or less.
  • the film of the present invention preferably contains a component containing elemental platinum and/or a component containing platinum cations.
  • the component containing elemental platinum is preferably simple platinum or an organic platinum compound.
  • the component containing platinum cations is preferably a platinum halide, platinum hydroxide, platinum alkoxide compound, platinum chelate compound, or platinum carboxylate.
  • the content of the platinum element in the film is preferably 0.010 mass ppm or more, more preferably 0.030 mass ppm or more, even more preferably 0.050 mass ppm or more, even more preferably 0.070 mass ppm or more, and 0.030 mass ppm or more. .10 mass ppm or more is particularly preferred.
  • the content of platinum element in the film is preferably 500 mass ppm or less, more preferably 300 mass ppm or less, even more preferably 100 mass ppm or less, even more preferably 50 mass ppm or less, and particularly preferably 30 mass ppm or less. , 10 mass ppm or less is particularly preferred.
  • the total content of ions containing platinum elements in the film is preferably 0.010 mass ppm or more, more preferably 0.030 mass ppm or more, even more preferably 0.050 mass ppm or more, and 0.070 mass ppm or more. is more preferable, and 0.10 mass ppm or more is particularly preferable.
  • the total content of ions containing platinum elements in the film is preferably 3,000 mass ppm or less, more preferably 1,000 mass ppm or less, further preferably 500 mass ppm or less, and still more preferably 300 mass ppm or less. It is preferably 100 mass ppm or less, particularly preferably 50 mass ppm or less.
  • the platinum element is coordinated to the surface of the member to be joined, and functions as an anchor at the interface with the member at extremely low temperatures. Therefore, it is estimated that the followability to each member is improved, and the adhesion and cooling/heating cycle reliability are improved.
  • the film of the present invention preferably satisfies at least one of the following conditions (S5a) and (S5b) from the viewpoint of improving adhesion at extremely low temperatures of about -50° C. and improving cooling/heating cycle reliability. From the same viewpoint, the film of the present invention more preferably satisfies the following condition (S5a), and even more preferably satisfies the following condition (S5a) and also satisfies the following condition (S5b).
  • the above-mentioned specific silicon compound preferably has a methyl group, phenyl group, hydroxy group, epoxy group, amino group, styryl group, (meth)acryloyl group, vinyl group, or allyl group.
  • the number of silicon atoms in the above-mentioned cyclic silicone compound is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. 10 or more is particularly preferred. On the other hand, the number of silicon atoms is preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less.
  • the specific silicon compound and cyclic silicone compound described above preferably have an alkoxy group and/or a silanol group.
  • the total number of the alkoxy groups and silanol groups is preferably one or more, more preferably two or more, and even more preferably three or more.
  • the total number of the alkoxy groups and silanol groups is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • the total content of specific silicon compounds in the film is preferably 0.010 mass ppm or more, more preferably 0.030 mass ppm or more, even more preferably 0.050 mass ppm or more, and 0.070 mass ppm or more. More preferably, 0.10 mass ppm or more is particularly preferred.
  • the total content of specific silicon compounds in the film is preferably 500 mass ppm or less, more preferably 300 mass ppm or less, further preferably 100 mass ppm or less, even more preferably 50 mass ppm or less, and 30 mass ppm or less. The following is particularly preferable, and 10 mass ppm or less is particularly preferable.
  • the total content of cyclic silicone compounds in the film is preferably 0.010 mass ppm or more, more preferably 0.030 mass ppm or more, even more preferably 0.050 mass ppm or more, and still more preferably 0.070 mass ppm or more.
  • 0.10 mass ppm or more is particularly preferable.
  • the total content of cyclic silicone compounds in the film is preferably 500 mass ppm or less, more preferably 300 mass ppm or less, further preferably 100 mass ppm or less, even more preferably 50 mass ppm or less, and 30 mass ppm or less. is particularly preferable, and particularly preferably 10 mass ppm or less.
  • the film of the present invention preferably contains a crosslinking agent or a compound having a structure derived from a crosslinking agent (hereinafter referred to as a "compound such as a crosslinking agent").
  • the compound such as a crosslinking agent may be a crosslinking agent or a compound having a structure derived from a crosslinking agent.
  • the crosslinking agent may be a compound in the composition for forming the film of the present invention.
  • the crosslinking agent refers to a compound having a crosslinkable group, a radically polymerizable group, a cationically polymerizable group, or an anionically polymerizable group that can react with a resin or the like.
  • the compound such as a crosslinking agent is preferably a compound that forms or has formed a crosslinked structure with the binder resin (SA).
  • SA binder resin
  • the crosslinking agent preferably has at least two alkoxymethyl groups, methylol groups, oxetanyl groups, blocked isocyanate groups, styryl groups, cinnamoyl groups, maleimide groups, nadimide groups, (meth)acryloyl groups, vinyl groups, or allyl groups.
  • the crosslinking agent is a compound different from the above-mentioned (SB) compound, and may be a compound having an epoxy group different from the above-mentioned (SB) compound.
  • crosslinking agents are suitable for improving the mechanical properties of the film due to the crosslinked structure formed with the (SA) binder resin. It is also presumed that adhesion and the like are improved due to interaction with each member due to the structure derived from the crosslinking agent.
  • the film of the present invention preferably contains a curing accelerator or a compound having a structure derived from a curing accelerator (hereinafter referred to as a "curing accelerator compound").
  • the compound such as a curing accelerator may be a curing accelerator, or may be a compound having a structure derived from a curing accelerator.
  • the curing accelerator may be a compound in the composition for forming the film of the present invention.
  • the curing accelerator refers to a compound having a structure that accelerates the reaction of the above-mentioned (SB) compound or crosslinking agent.
  • the compound such as a curing accelerator is preferably a compound that forms or has formed a crosslinked structure with the above-mentioned (SB) compound or crosslinking agent.
  • the crosslinked structure is preferably formed by reaction, and is not particularly limited, and may be formed by heating, irradiation with energy rays, etc.
  • the curing accelerator preferably has an imidazole group, a polyhydric phenol structure, an acid anhydride group, a hydrazide group, a mercapto group, or a Lewis acid-amine complex structure.
  • the curing accelerator is a compound different from the above-mentioned (SC) compound, and may be a compound having an amino group different from the above-mentioned (SC) compound.
  • the curing accelerator is also preferably a latent curing accelerator that releases the above-mentioned substituents or structures by reaction, heating, or irradiation with energy rays.
  • the above compounds such as curing accelerators are suitable for improving the mechanical properties of the film due to the crosslinked structure formed with the (SB) compound or crosslinking agent. It is also presumed that adhesion and the like are improved due to interaction with each member due to the structure derived from the curing accelerator.
  • the curing accelerator is preferably a compound that has a silicone structure and/or a siloxane structure, has at least two alkylene groups bonded to silicon atoms in the silicone structure or siloxane structure, and further has an acid anhydride group (hereinafter referred to as "specific acid anhydride compound").
  • the silicone structure and siloxane structure of a specific acid anhydride compound are bonded to at least two alkylene groups, and are preferably divalent or higher-valent structures via these alkylene groups.
  • the number of silicon atoms that the specific acid anhydride compound has is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, and particularly preferably 20 or more.
  • the number of silicon atoms contained in the specific acid anhydride compound is preferably 30 or less.
  • the silicone structure in the specific acid anhydride compound is preferably a dialkyl silicone structure and/or a monoalkyl silicone structure.
  • the siloxane structure in the specific acid anhydride compound is preferably a monoalkylsiloxane structure.
  • the above-mentioned specific acid anhydride compound has a flexible skeleton derived from a silicone structure or a siloxane structure, and/or has a shear strain at -50°C adjusted to within a range of 0.70 to 20. It is suitable for adjusting the elastic modulus within the range of 0.10 to 200 MPa.
  • the film of the present invention may contain other compounds or compounds having structures derived from other compounds. These compounds may be other compounds or may have structures derived from other compounds. Other compounds may be compounds in the composition for forming the film of the present invention. Other compounds are preferably metal alkoxide compounds, metal chelate compounds, or surfactants.
  • the metal alkoxide compound and the metal chelate compound preferably contain titanium, zirconium, aluminum, magnesium, zinc, indium, tin, or copper as a main component element.
  • the above metal alkoxide compounds and metal chelate compounds are suitable for improving the mechanical properties of the film due to the crosslinked structure formed with the (SA) binder resin, (SB) compound, or crosslinking agent. Furthermore, since these compounds function as anchors at the interface with the member, it is presumed that adhesion and the like are improved.
  • the surfactant is preferably a fluororesin surfactant, a silicone surfactant, or an acrylic resin surfactant.
  • the above-mentioned surfactants are suitable for bonding another member to the surface of the film because they suppress protrusions on the surface of the film. It is presumed that by suppressing protrusions on the surface, adhesion and the like are improved due to an increase in the contact area and interaction with another member.
  • the solvent is preferably a compound having an alcoholic hydroxyl group, a carbonyl group, an ester bond, an amide bond, or at least three ether bonds.
  • a method for producing a composition for forming the film of the present invention will be exemplified. Examples include a method in which a resin, various additives, filler components, and a solvent are added, mixed using a stirrer or kneader, and then mixed using a bead mill, three-roll mill, or the like.
  • the method for manufacturing the film of the present invention will be exemplified. After forming a coating film of the composition on a support described below by a method such as coating or printing, the coating film is dried under reduced pressure to distill off the solvent, if necessary, and then the coating film is An example is a method of heating at °C. Thereafter, a protective film, which will be described later, may be laminated on the formed film, if necessary.
  • the elastic modulus at -50°C is preferably 0.10 to 200 MPa.
  • the elastic modulus at -50°C is preferably 0.10 MPa or more, more preferably 0.30 MPa or more, even more preferably 0.50 MPa or more, even more preferably 0.70 MPa or more, and particularly preferably 1.0 MPa or more, from the viewpoint of improving adhesion at a cryogenic temperature of about -50°C and improving reliability in cold-heat cycles.
  • the elastic modulus at -50°C is preferably 200 MPa or less, more preferably 130 MPa or less, and even more preferably 100 MPa or less, from the viewpoint of improving adhesion at a cryogenic temperature of about -50°C and improving reliability in cold-heat cycles. Furthermore, the elastic modulus at -50°C is preferably 50 MPa or less, more preferably 30 MPa or less, even more preferably 10 MPa or less, and particularly preferably 5.0 MPa or less.
  • the internal stress caused by the difference in thermal expansion coefficient between the members to which the film is bonded can be reduced by lowering the elastic modulus at extremely low temperatures of around -50°C, allowing the film to follow each member. It is presumed that this improves adhesion and cooling/heating cycle reliability.
  • the film of the present invention has a thermal conductivity of 0.10 to 5.0 W/(m ⁇ K) at 25°C.
  • the thermal conductivity at 25°C is preferably 0.30 W/(m ⁇ K) or more, and 0.50 W/(m ⁇ K) or more from the viewpoint of improving adhesion and improving cooling/heating cycle reliability. It is more preferably 0.70 W/(m ⁇ K) or more, even more preferably 1.0 W/(m ⁇ K) or more.
  • the thermal conductivity at 25° C. is preferably 4.0 W/(m ⁇ K) or less, more preferably 3.0 W/(m ⁇ K) or less, and 2.5 W/(m ⁇ K) or less from the viewpoint of improving cooling/heating cycle reliability. (m ⁇ K) or less is more preferable, and 2.0 W/(m ⁇ K) or less is particularly preferable.
  • the first embodiment of the film of the present invention has a shear strain of 0.70 to 20 at -50°C.
  • the second embodiment of the film of the present invention preferably has a shear strain of 0.70 to 20 at -50°C.
  • the shear strain at -50°C is preferably 1.0 or more, more preferably 1.5 or more, from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability. 2.0 or more is more preferable, and 2.5 or more is particularly preferable.
  • the shear strain at -50°C is preferably 17 or less, more preferably 15 or less, even more preferably 12 or less, from the viewpoint of improving adhesion and improving thermal cycle reliability at extremely low temperatures of about -50°C. 10 or less is particularly preferred.
  • the thickness of the film of the present invention is preferably 5.0 ⁇ m or more, more preferably 20 ⁇ m or more, even more preferably 50 ⁇ m or more, even more preferably 100 ⁇ m or more, and particularly preferably 150 ⁇ m or more.
  • the thickness of the film of the present invention is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, even more preferably 350 ⁇ m or less, particularly preferably 300 ⁇ m or less, from the viewpoint of improving thermal cycle reliability.
  • the laminate of the present invention will be described below. Note that when describing the laminate of the present invention, the description is common to the first and third embodiments of the laminate of the present invention having the film of the present invention. On the other hand, when describing a specific embodiment of the laminate, it will be described as a first embodiment of the laminate of the present invention. However, the present invention is not limited to the following embodiments, and various changes can be made without departing from the gist of the invention and which can achieve the purpose of the invention.
  • the elastic modulus at 25°C is preferably 0.010 MPa or more, more preferably 0.050 MPa or more, even more preferably 0.10 MPa or more, particularly preferably 0.30 MPa or more, from the viewpoint of improving adhesion.
  • the elastic modulus at 25° C. is preferably 1.0 MPa or less, more preferably 0.70 MPa or less, and even more preferably 0.50 MPa or less, from the viewpoint of improving adhesion.
  • the film of the present invention is preferably in a semi-cured state (B stage).
  • the semi-cured state refers to a state in which the film has fluidity, although no crosslinked structure is formed, or a crosslinked structure is partially formed by reaction.
  • the coating film is dried under reduced pressure to distill off the solvent, or the coating film is heated and dried at 40 to 150°C. refers to the state in which it is soluble in
  • a first embodiment of the laminate of the present invention is a laminate having a support and the film of the present invention, in which the film of the present invention is disposed on the support.
  • the elastic modulus of the film at 25° C. is preferably 0.010 to 1.0 MPa, and the film is preferably in a semi-cured state.
  • the above-mentioned configuration is preferable from the viewpoints of improving adhesion and ease of handling, and is suitable for placing the film on a base member or ceramic dielectric member, which will be described later.
  • the first aspect of the laminate of the present invention has a support.
  • the support is preferably a flexible substrate from the viewpoints of improved adhesion with the film, flexibility, and handling.
  • the flexible substrate is preferably a polyimide substrate, a polyphenylene sulfide substrate, a silicone substrate, an acrylic resin substrate, an epoxy resin substrate, a polyethylene terephthalate substrate, a polybutylene terephthalate substrate, a polyethylene naphthalate substrate, or a polycarbonate substrate.
  • the support may be a rigid substrate. Examples of the rigid substrate include a glass substrate, a quartz substrate, a crystal substrate, or a sapphire substrate.
  • the surface of the support on the film side may be treated with a silane coupling agent or the like from the viewpoint of improving adhesion to the film and improving releasability.
  • the thickness of the support is preferably 10 to 200 ⁇ m from the viewpoint of handling properties.
  • the first aspect of the laminate of the present invention is preferably a laminate having a first support, a film of the present invention, and a second support in this order from the viewpoint of improving handling properties and protecting the surface of the film. . Further, it is preferable that the first support and the second support have different thicknesses.
  • the second support is preferably a protective film, and preferably a polyethylene film, a polypropylene film, a polyester film, a polyethylene terephthalate film, a polybutylene terephthalate film, or a polyethylene naphthalate film. From the viewpoint of handling properties, the second support preferably has a low adhesive strength with the film.
  • FIG. 1 shows a schematic cross-sectional view of a configuration example of the first embodiment of the laminate.
  • a laminate 100A shown in FIG. 1 is a laminate having a first support 10, a film 30 of the present invention, and a second support 20 in this order.
  • the first support 10 and the second support 20 are as described above.
  • the film 30 is the film of the present invention, and is preferably in a semi-cured state (B stage).
  • the film 30 is preferably a layer formed from a composition for forming the film of the present invention.
  • the film of the present invention is preferably a cured product of the composition.
  • the composition is preferably a composition for forming the film of the present invention.
  • Curing refers to the formation of a crosslinked structure due to reaction and the loss of fluidity of the film, and also refers to that state.
  • the reaction is not particularly limited, such as by heating or irradiation with energy rays, but preferably by heating.
  • the state in which a crosslinked structure is formed by heating and the film loses its fluidity is called thermosetting.
  • the heating conditions include, for example, heating at 150 to 500° C. for 5 to 300 minutes.
  • Examples of the heating method include heating using an oven, a hot plate, infrared rays, a flash annealing device, or a laser annealing device.
  • the processing atmosphere may be, for example, air, oxygen, nitrogen, helium, neon, argon, krypton, or xenon atmosphere, with oxygen in an amount of 1.0 mass ppm or more and less than 10,000 mass ppm (0.00010 mass % or more and 1.0 mass ppm). %), a gas atmosphere containing 10,000 mass ppm (1.0 mass %) or more of oxygen, or a vacuum.
  • the film of the present invention can have both high adhesion for joining members together even at extremely low temperatures of about -50°C and high thermal cycle reliability. Therefore, the film of the present invention is preferably used in a substrate processing step at a temperature of 0° C. or lower, and more preferably used for forming a laminate in which a substrate processing step is performed at a temperature of 0° C. or lower.
  • the temperature of the substrate processing step in which the laminate is used is more preferably -20°C, even more preferably -40°C or lower, even more preferably -50°C or lower, and particularly preferably -60°C or lower.
  • the temperature in the above substrate processing step is preferably -150°C or higher, more preferably -100°C or higher, and even more preferably -80°C or higher.
  • the substrate processing step is preferably one or more selected from the group consisting of sputtering, vapor deposition, chemical vapor deposition, ion implantation, etching, ashing, exposure, and inspection.
  • the film of the present invention may be used in a substrate processing step at a temperature exceeding 0°C, or may be used for forming a laminate in which a substrate processing step is performed at a temperature exceeding 0°C.
  • the temperature of the substrate processing step in which the laminate is used is preferably 20°C or higher, more preferably 40°C or higher, and even more preferably 60°C or higher.
  • the temperature in the substrate processing step is preferably 150°C or lower, more preferably 100°C or lower, and even more preferably 80°C or lower.
  • the film has a plurality of through holes.
  • the method for forming the through holes is preferably a punch hole method, a press method, a laser processing method, a laser direct imaging method, a laser direct structuring method, a printing method, an inkjet method, an etching method, or a photolithography method.
  • a second aspect of the laminate of the present invention is a laminate having a base member, a film of the present invention, and a ceramic dielectric member in this order, the base member and the ceramic dielectric member having different coefficients of thermal expansion. It is a laminate.
  • the film is preferably a cured product of the composition.
  • the elastic modulus of the film at 25° C. is 0.010 to 1.0 MPa, and it is also preferable that the film is in a semi-cured state.
  • the above-mentioned configuration is suitable from the viewpoint of improving adhesion when joining a base member and a ceramic member, and has a significant effect of preventing separation of the members even when the thermal expansion coefficients of the base member and the ceramic dielectric member are different.
  • the difference in thermal expansion coefficient between the base member and the ceramic dielectric member is preferably 1.0 ppm/K or more, more preferably 5.0 ppm/K or more, and 10 ppm or more from the viewpoint of improving adhesion and heat dissipation efficiency in the substrate processing process. /K or more is more preferable.
  • the above-mentioned difference in thermal expansion coefficient is preferably 30 ppm/K or less, more preferably 25 ppm/K or less, and even more preferably 20 ppm/K or less.
  • the films included in the laminate of the present invention are similar to the films of the present invention (S1a), (S2a), and (S3a) from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability. ), (S1b), (S2b), and (S3b).
  • the film included in the laminate of the present invention preferably contains the above (I) and/or (II) similarly to the film of the present invention.
  • the preferable range of the content of boron element, the preferable range of the content of phosphorus element, and the preferable range of the total content of chlorine element and bromine element in the film of the laminate are also the same as in the film of the present invention.
  • Preferred range of total content of ions containing boron element in the film of the laminate, preferred range of total content of ions containing phosphorus element, and preferred total content of chloride ion and bromide ion The ranges are also the same as above.
  • the film included in the laminate of the present invention satisfies the above conditions (S4a) and (S4b) similarly to the film of the present invention from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability. It is preferable that at least one of these conditions is satisfied.
  • the film of the laminate of the present invention preferably contains a component containing a platinum element and/or a component containing a platinum cation, similarly to the film of the present invention.
  • the preferred range of the platinum element content in the film of the laminate is also the same as that of the film of the present invention.
  • the preferred range of the total content of ions containing elemental platinum in the film of the laminate is also the same as that of the film of the present invention.
  • the film included in the laminate of the present invention satisfies the conditions of (S5a) and (S5b) above in the same way as the film of the present invention from the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving reliability of cooling and heating cycles. It is preferable that at least one of these conditions is satisfied.
  • examples and preferable descriptions regarding specific silicon compounds and cyclic silicone compounds are also as described above.
  • the preferred range of the total content of specific silicon compounds in the film of the laminate and the preferred range of the total content of cyclic silicone compounds are also the same as above.
  • a second aspect of the laminate of the present invention has a base member.
  • the base member is made of metal and various composite materials.
  • the metal is preferably aluminum, titanium, or an alloy thereof.
  • the composite material is preferably one in which an aluminum alloy containing aluminum as a main component is melted and infiltrated under pressure into a porous ceramic containing silicon carbide as a main component.
  • the aluminum alloy in the composite material may contain silicon or magnesium, and may also contain other elements.
  • a second aspect of the laminate of the present invention includes a ceramic dielectric member.
  • the ceramic dielectric member is preferably a flat base material made of sintered ceramic.
  • Ceramic dielectric members are made of aluminum oxide (alumina: Al 2 O 3 ), aluminum nitride, silicon carbide, silicon nitride, and silicon oxide from the viewpoints of mechanical strength, wear resistance, plasma resistance, thermal conductivity, and insulation properties. It is preferable to contain at least one type selected from the group consisting of yttrium (Y 2 O 3 ), and more preferably to contain aluminum oxide or aluminum nitride as a main component. Note that the main component refers to the component that is contained in the largest amount based on mass among the constituent components.
  • FIG. 2 shows a schematic cross-sectional view of a configuration example of the second embodiment of the laminate.
  • a laminate 200A shown in FIG. 2 is a laminate including a base member 40, a film 60 of the present invention, and a ceramic dielectric member 50 in this order.
  • the base member 40 and the ceramic dielectric member 50 are as described above.
  • the film 60 is the film of the present invention, and is preferably a cured product of the composition.
  • the film 60 is preferably a layer formed from a composition for forming the film of the present invention.
  • the electrostatic chuck of the present invention includes a laminate having the film of the present invention. Furthermore, the film of the present invention can have both high adhesion for joining members together even at extremely low temperatures of about -50° C. and high thermal cycle reliability. Therefore, the film of the present invention is preferably used in a substrate processing step at a temperature of 0° C. or lower, and more preferably used for forming an electrostatic chuck in a substrate processing step at a temperature of 0° C. or lower. That is, the film of the present invention is suitable for use in electrostatic chucks.
  • the film of the present invention is particularly suitable for use in electrostatic chucks used at temperatures below 0°C, and further particularly suitable for uses in electrostatic chucks used at temperatures below -50°C.
  • the preferable temperature range for the substrate processing step in which the electrostatic chuck is used is also the same as the temperature in the substrate processing step in which the above-described laminate is used.
  • the substrate processing step is preferably one or more selected from the group consisting of sputtering, vapor deposition, chemical vapor deposition, ion implantation, etching, ashing, exposure, and inspection.
  • the film of the present invention may be used in a substrate processing step at a temperature exceeding 0° C., or may be used for forming an electrostatic chuck in a substrate processing step at a temperature exceeding 0° C.
  • the preferable temperature range of the substrate processing step in which the electrostatic chuck is used is also the same as the temperature in the substrate processing step in which the above-described laminate is used.
  • the laminate of the present invention can be applied to various articles.
  • Such an article is preferably one that includes an electrostatic chuck that includes the laminate of the present invention.
  • Examples of the article including the above-mentioned laminate or the article including the electrostatic chuck include electronic devices, moving objects, buildings, windows, and the like.
  • Examples of electronic devices include display devices, semiconductor devices, metal-clad laminates, industrial devices, medical devices, and construction devices.
  • Examples of moving objects include vehicles, trains, airplanes, and heavy machinery.
  • buildings include residences, stores, offices, buildings, and factories.
  • Examples of the window include an electronic device window, a mobile object window, and a building window.
  • the plasma processing apparatus of the present invention includes a plasma generation source and the laminate of the present invention.
  • the plasma processing apparatus of the present invention preferably includes a plasma generation source and an electrostatic chuck including the laminate of the present invention.
  • Such a configuration is suitable from the viewpoint of improving the aspect ratio and reducing the process time in the etching process, and is preferably used for increasing the density and integration of 3D-NAND memories and the like.
  • the plasma processing apparatus of the present invention places a substrate to be processed, such as a semiconductor wafer, on a laminate (preferably an electrostatic chuck) provided in a vacuum chamber, and generates plasma by applying a high frequency voltage in a vacuum environment.
  • a laminate preferably an electrostatic chuck
  • An electrostatic chuck in a plasma processing device is a laminate made by bonding a ceramic dielectric member with a built-in heater electrode and an electrostatic electrode, and a base member, which is a cooling plate with a coolant flow path formed inside, using a film. be.
  • a plasma processing apparatus is equipped with a mounting table on which a semiconductor wafer is placed inside a vacuum chamber, and the mounting table mainly consists of an electrostatic chuck and a cooler that controls the temperature of the electrostatic chuck.
  • the mounting table mainly consists of an electrostatic chuck and a cooler that controls the temperature of the electrostatic chuck.
  • high processing accuracy has been required in the manufacture of semiconductor devices, and forming vias with high aspect ratios requires etching processing at extremely low temperatures of ⁇ 30° C. or lower. Therefore, it is necessary to cool the base member, which is a cooling plate, to ⁇ 30° C. or lower to cool the ceramic dielectric member.
  • the film of the present invention that joins these components can reduce the thermal resistance at the interface between the two members, thereby making it possible to improve cooling efficiency.
  • Articles comprising the film of the present invention and laminates comprising the film of the present invention are also suitable for use in applications other than electrostatic chucks.
  • other uses include, for example, vacuum chucks.
  • the method for manufacturing a laminate of the present invention includes the steps of arranging a base member, arranging a film of the invention, and arranging a ceramic dielectric member.
  • the step of arranging the film of the present invention is preferably performed after the step of arranging the base member, and preferably on the base member. That is, the method for manufacturing a laminate of the present invention includes the step of disposing the film of the present invention after the step of disposing the base member, and the step of disposing the ceramic dielectric member after the step of disposing the film of the present invention.
  • the step of arranging is preferred.
  • the step of arranging the film of the present invention is also preferable after the step of arranging the ceramic dielectric member, and it is also preferable to arrange it on the ceramic dielectric member. That is, the method for manufacturing a laminate of the present invention includes the step of disposing the film of the present invention after the step of disposing the ceramic dielectric member, and the step of disposing the base member after the step of disposing the film of the present invention. The step of arranging is also preferable.
  • the step of arranging the base member is preferably a step of arranging the base member on the article, and is also preferably a step of arranging the base member fixed to the article.
  • the step of arranging the base member is also preferably a step of forming the base member on a support, arranging the base member having the support, and then peeling the support from the base member.
  • the base member having the support is preferably arranged by bonding with an adhesive or the like.
  • Examples of the article include electronic devices, moving objects, buildings, windows, and the like.
  • Examples of electronic devices include display devices, semiconductor devices, metal-clad laminates, industrial devices, medical devices, and construction devices.
  • Examples of moving objects include vehicles, trains, airplanes, and heavy machinery.
  • Examples of buildings include residences, stores, offices, buildings, and factories.
  • Examples of the window include an electronic device window, a mobile object window, and a building window.
  • the base member may be a commercially available metal member.
  • the step of arranging the base member may be a step of arranging a commercially available metal member as the base member on the article.
  • the step of arranging the ceramic dielectric member is preferably a step of arranging the ceramic dielectric member on the article.
  • the step of arranging the ceramic dielectric member is after the step of arranging the film of the present invention, it is preferably arranged on the film of the present invention.
  • the step of arranging the ceramic dielectric member is preferably a step of forming the ceramic dielectric member on the support, arranging the ceramic dielectric member having the support, and then peeling the support from the ceramic dielectric member. It is preferable that the ceramic dielectric member having the support body is bonded together using an adhesive or the like.
  • the article include the article exemplified in the above-mentioned base member.
  • the ceramic dielectric member may be a commercially available ceramic member.
  • the step of arranging the ceramic dielectric member may be a step of arranging a commercially available ceramic member as the ceramic dielectric member on the article.
  • the step of arranging the film of the present invention is preferably a step of bonding the film of the present invention by thermocompression bonding, and preferably bonding the film by thermocompression bonding onto the base member. Similarly, it is also preferable to bond by thermocompression bonding onto a ceramic dielectric member. Further, in the step of arranging the base member, it is also preferable to bond the base member to the film of the present invention by thermocompression bonding. Similarly, in the step of arranging the ceramic dielectric member described above, it is also preferable to bond the ceramic dielectric member onto the film of the present invention by thermocompression bonding.
  • the preferred method for joining by thermocompression is hot press treatment, hot lamination treatment, or hot vacuum lamination treatment.
  • the first support may be peeled off after the film of the present invention is placed, or may be peeled off during or after the film of the present invention is bonded by a method such as thermocompression bonding.
  • ABPS Bis(3-amino-4-hydroxyphenyl) sulfone
  • BAHF 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane
  • BAP 2,2-bis(3-amino-4-hydroxyphenyl) )
  • BAPF 9,9-bis(3-amino-4-hydroxyphenyl)fluorene
  • cyEpoTMS 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane
  • DMeDMS Dimethyldimethoxysilane
  • DPhDMS Diphenyldimethoxysilane
  • polyimides (PI-2) to (PI-11) were prepared from each resin by the method described in Synthesis Example 1 above, changing the monomer compound and copolymerization ratio as appropriate. Synthesized. The copolymerization ratio of monomers is shown in Table 1.
  • Synthesis Example 12 Synthesis of silicone resin (SR-1) In a three-necked flask, add 52.30 g (87 mol%) of DMeDMS, 2.73 g (3 mol%) of DPhDMS, 3.41 g (5 mol%) of MeTMS, and 6.16 g of cyEpoTMS. (5 mol%) and 61.63 g of PGMEA were charged. Air was flowed into the flask at a rate of 0.05 L/min, and the mixed solution was heated to 40° C. in an oil bath while stirring. While further stirring the mixed solution, an aqueous phosphoric acid solution prepared by dissolving 0.194 g of phosphoric acid in 19.37 g of water was added over 10 minutes.
  • SR-1 silicone resin
  • the mixture was stirred at 40° C. for 30 minutes to hydrolyze the silane compound.
  • the bath temperature was raised to 70°C and stirred for 1 hour, and then the bath temperature was raised to 115°C.
  • the internal temperature of the solution reached 100°C about 1 hour after the start of temperature rise, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C).
  • the resin solution obtained by heating and stirring for 2 hours was cooled in an ice bath to obtain a silicone resin (SR-1) solution with a solid content concentration of 40% by mass.
  • the weight average molecular weight of the obtained silicone resin was 4,000.
  • silicone resins (SR-2) to (SR-4) were prepared using each resin by the method described in Synthesis Example 12 above, changing the monomer compound and copolymerization ratio as appropriate. was synthesized. The copolymerization ratio of monomers is shown in Table 2.
  • Synthesis Example 16 Synthesis of polysiloxane (PS-1) In a three-neck flask, 38.82 g (57 mol%) of MeTMS, 2.97 g (3 mol%) of PhTMS, 21.04 g (35 mol%) of DMeDMS, and 6.16 g of cyEpoTMS (5 mol%) and 57.15 g of PGMEA were charged. Air was flowed into the flask at a rate of 0.05 L/min, and the mixed solution was heated to 40° C. in an oil bath while stirring. While further stirring the mixed solution, an aqueous phosphoric acid solution prepared by dissolving 0.207 g of phosphoric acid in 24.33 g of water was added over 10 minutes.
  • the mixture was stirred at 40° C. for 30 minutes to hydrolyze the silane compound.
  • the bath temperature was raised to 70°C and stirred for 1 hour, and then the bath temperature was raised to 115°C.
  • the internal temperature of the solution reached 100°C about 1 hour after the start of temperature rise, and from there it was heated and stirred for 2 hours (internal temperature was 100 to 110°C).
  • the resin solution obtained by heating and stirring for 2 hours was cooled in an ice bath to obtain a polysiloxane (PS-1) solution with a solid content concentration of 40% by mass.
  • the weight average molecular weight of the obtained polysiloxane was 5,500.
  • polysiloxanes (PS-2) to (PS-4) were prepared by using each resin according to the method described in Synthesis Example 16 above, changing the monomer compound and copolymerization ratio as appropriate. Synthesized. The copolymerization ratio of monomers is shown in Table 2.
  • Polyimide (PI-1) ⁇ (PI-7) These polyimides have a main chain containing a polyimide structure, a diamine residue having a structure represented by general formula (11), and a tetracarboxylic acid anhydride residue having a structure represented by general formula (12). have The content of fluorine element in the resin structure of these polyimides is 29,300 mass ppm for (PI-1), 15,600 mass ppm for (PI-2), and 4 for (PI-3). , 700 mass ppm, (PI-4) 3,100 mass ppm, (PI-5) 3,300 mass ppm, (PI-6) 5,400 mass ppm, (PI-7) 6,200 mass ppm Mass ppm.
  • Polyimides (PI-8) to (PI-10) These polyimides have a main chain containing a polyimide structure, a diamine residue having a structure represented by general formula (11), and a tetracarboxylic anhydride residue having a structure represented by general formula (12).
  • the content of fluorine element in the resin structure of these polyimides is 0.000 ppm by mass.
  • Polyimide (PI-11) This polyimide has a main chain that includes a polyimide structure.
  • the content of fluorine element in the resin structure of this polyimide is 168,500 ppm by mass.
  • Silicone resin (SR-1) ⁇ (SR-4) These silicone resins have a main chain containing a silicone resin structure, bifunctional organosilane units and trifunctional organosilane units having an aliphatic group, trifunctional organosilane units having an aromatic group, and trifunctional organosilane units having an epoxy group. It has a silane unit.
  • Polysiloxane (PS-1) ⁇ (PS-4) These polysiloxanes have a main chain containing a polysiloxane structure, bifunctional organosilane units and trifunctional organosilane units having an aliphatic group, trifunctional organosilane units having an aromatic group, and trifunctional organosilane units having an epoxy group. It has a silane unit.
  • Detector Waters 996 System controller: Waters 2690 Column oven: Waters HTR-B Thermo controller: Waters TCM Column: TOSOH Guard Column Column: TOSOH TSK-GEL ⁇ -4000 Column: TOSOH TSK-GEL ⁇ -2500 Fluidized bed: N-methyl-2-pyrrolidone in which lithium chloride and phosphoric acid were each dissolved at 0.050 mol/L. Development rate: 0.40 mL/min.
  • the above silicone resins (SR-1) to (SR-4) and the above polysiloxanes (PS-1) to (PS-4) were analyzed using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) in a fluidized bed.
  • the weight average molecular weight in terms of polystyrene was determined by using tetrahydrofuran or N-methyl-2-pyrrolidone at room temperature in accordance with "JIS K7252-3 (2008)".
  • volume content ratio of filler in film The film was heated at 800°C to thermally decompose and/or volatilize organic components such as resin. The mass of the remaining filler was measured, and the mass of the organic components such as resin was calculated from the difference. The obtained mass was divided by the specific gravity of each component to obtain the volume of each component. The volume content ratio of the filler was calculated by taking the total volume of each component as 100 volume%.
  • ⁇ Combustion/absorption conditions> System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation) Electric furnace temperature: Inlet 900°C, Outlet 1000°C Gas: Ar/ O2 200mL/min, O2 400mL/min Absorption liquid: H 2 O 2 0.1% by mass Absorption liquid volume: 5mL ⁇ Ion chromatography/anion analysis conditions> System: ICS1600 (manufactured by DIONEX) Mobile phase: 2.7 mmol/L Na 2 CO 3 , 0.3 mmol/L NaHCO 3 Flow rate: 1.50mL/min Detector: Electrical conductivity detector Injection volume: 100 ⁇ L.
  • Elemental platinum content in the film The content of elemental platinum was measured by inductively coupled plasma mass spectrometry and inductively coupled plasma emission spectrometry using a calibration curve based on a standard substance.
  • ⁇ Filtration processing conditions Membrane filter: 0.22 ⁇ m ⁇ , PVDF (manufactured by Merck Millipore) Solid phase extraction cartridge: InertSep Slim-J PLS-3 (manufactured by GL Sciences) Cation exchange cartridge: OnGuard II H (manufactured by Thermo Fisher Scientific) ⁇ Ion chromatography analysis conditions> Device: ICS-5000 + (manufactured by Thermo Fisher Scientific) Separation column: 2mm ⁇ x 250mm, IonPac AS11-HC-4 ⁇ m Eluent: potassium hydroxide/gradient Detector: conductivity detector Sample injection volume: 100 ⁇ L.
  • Elastic modulus of film A 250 ⁇ m thick film, which is a cured film of the composition, was prepared on a 38 ⁇ m thick PET film using the method described in Example 1 below. Peel off the PET film, cut the film into a shape of 5.0 mm width x 30 mm length, and measure the elastic modulus of the film using a dynamic viscoelasticity measurement device (DVA-200; manufactured by IT Keizai Control Co., Ltd.) did. The measurement conditions were a heating rate of 5.0°C/min and a measurement frequency of 1Hz, and the storage modulus was measured at each temperature from -100 to 300°C, and the elastic modulus at -50°C was determined.
  • DVA-200 dynamic viscoelasticity measurement device
  • the obtained laminate was subjected to a shear test based on "JIS K6850".
  • the test conditions were a temperature of -50°C and a tensile rate of 2.0 mm/min, and the stress and shear deformation at break were measured.
  • the shear strain at -50°C was calculated from the shear deformation, and the stress at break was taken as the shear adhesive strength at -50°C as an index of bonding adhesion.
  • A+, A, B+, B, C+, and C with shear adhesive strength of 0.5 MPa or more are accepted, and A+, A, B+, and C with shear adhesive strength of 1.5 MPa or more.
  • B was evaluated as good, and A+ and A with shear adhesive strength of 1,000 or more were evaluated as excellent.
  • B+ Shear adhesive strength is 2.0 or more and less than 2.5
  • Shear adhesive strength is 1.
  • Shear adhesive strength is 1.0 or more and less than 1.5 C: Shear adhesive strength is 0.5 or more and less than 1.0 D: Shear adhesive strength is 0.1 or more , and less than 0.5 E: Shear adhesive strength is less than 0.1 or unmeasurable.
  • a semi-cured film of the composition was prepared on a 38 ⁇ m thick PET film using the method described in Example 1 below so that the cured film had a thickness of 250 ⁇ m. .
  • the laminate on which the semi-cured film was formed was cut into a shape of 150 mm in diameter, and heat laminated on a 100 mm in diameter and 3.0 mm thick aluminum plate at 60° C. and 0.10 MPa.
  • the PET film was peeled off, and an alumina substrate having a diameter of 100 mm and a thickness of 3.0 mm was laminated and heat press treated at 120° C. and 0.50 MPa for 24 hours to produce a laminate.
  • (SB) compound (sb-1) used in each example, reference example, and comparative example (SC) compound (sc-1), (sc-2), (sc-3), Compounds corresponding to (sc-4), (ad-1), which is a curing accelerator, and (r-1), which is an amine compound used in the comparative example, are also shown below.
  • (sb-1) has a weight average molecular weight of 870 and an epoxy group equivalent of 435 g/mol.
  • chloride ions, bromide ions, ions containing elemental platinum, or fluoride ions hereinafter referred to as "specific element compounds”
  • specific silicon compounds the above-mentioned specific silicon compounds
  • cyclic silicone compounds compounds corresponding to each of them; are also shown below.
  • B-1) Triphenyl borate (B-2): Tetraethylammonium tetrafluoroborate
  • P-1 Triphenylphosphine
  • P-2 Tetraethylammonium phosphate
  • Cl-1) Benzyl chloride
  • Cl-2) Tetraethylammonium chloride
  • Br-1 Benzyl bromide
  • Pt-1 Simple platinum
  • Pt-2 Acetylacetonate Platinum
  • Si-1 Dimethyldimethoxysilane
  • Si-3 Octamethylcyclotetrasiloxane
  • Si-4 Octaphenylcyclotetrasiloxane
  • F-1) Dodecyl fluoride
  • F-2) Ammonium fluoride (butyltriethyl).
  • compositions 1 to 67 used for film formation were prepared using the compositions shown in Tables 3 to 10.
  • Tables 3 to 10 the numbers in parentheses indicate parts by mass of the solid content of each component. After mixing each component, the mixture was repeatedly kneaded five times using a three-roll mill to obtain a viscous liquid composition.
  • Compositions 1 to 67 contain TEGDM contained in each of the above polyimide solutions as a solvent, and Compositions 22 to 29 contain TEGDM contained in each of the above silicone resin solutions or the above polysiloxane solutions as a solvent.
  • Contains PGMEA Note that the solid content concentration of Composition 1 was 87% by mass.
  • the amount of the specific element compound added depends on the content of boron, phosphorus, chlorine, bromine, platinum, and fluorine in the composition, as well as ions containing boron, ions containing phosphorus, and chloride.
  • the compositions were prepared so that the contents of compound ions, bromide ions, ions containing elemental platinum, and fluoride ions were as shown in Tables 3 to 10.
  • the amounts of specific silicon compounds and cyclic silicone compounds added were adjusted to give the compositions shown in Tables 3 to 10.
  • Example 1 ⁇ Preparation of film evaluation sample> Composition 1 was applied onto a 38 ⁇ m thick PET film using a comma roll coater so that the cured film had a thickness of 250 ⁇ m, and then dried at 100° C. for 30 minutes to form a film. A semi-cured film was prepared. The produced semi-cured film was heated at 180° C. for 4 hours to produce a cured film of Composition 1 with a thickness of 250 ⁇ m.
  • Examples 2 to 64 and Comparative Examples 1 to 3 The same operations and evaluations as in Example 1 were performed using each of the compositions shown in Tables 3 to 10. These evaluation results are summarized in Tables 11 to 18. For ease of comparison, Tables 12 to 15 and Table 17 show the evaluation results of Example 3, and Table 16 shows the evaluation results of Example 8. The contents of the fluorine element in the compositions in Examples 1 to 7, Examples 11 to 21, Examples 30 to 64, and Comparative Examples 1 to 3 are shown in Table 3 and Table 3. 4 and Tables 6 to 10, and the content of elemental fluorine in the film is as shown in Table 11, Table 12, and Tables 14 to 18.
  • Comparative Example 1 contains (r-1) as an amine compound instead of the (SC) compound, and because (r-1) has poor flexibility, the elastic modulus of the film at -50°C is much higher than 200 MPa. , the shear strain at -50°C is also less than 0.70. Therefore, the film has poor thermal cycle reliability.
  • Comparative Example 2 does not contain the (SC) compound, and the elastic modulus at -50°C is outside the range of 0.10 to 200 MPa, and the shear strain at -50°C is also outside the range of 0.70 to 20. . Therefore, the film has poor thermal cycle reliability characteristics.
  • Comparative Example 3 contains polyimide (PI-11) as the (SA) binder resin. Since polyimide (PI-11) has poor flexibility, the elastic modulus of the film at -50°C is extremely large, and the shear strain at -50°C is extremely small. Therefore, the film has poor thermal cycle reliability.
  • First support body 20
  • Second support body 30
  • Base member 50
  • Ceramic dielectric member 60

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)

Abstract

La présente invention aborde le problème qui consiste à fournir un film qui présente une excellente adhérence pour des éléments de liaison, même à une température extrêmement basse d'environ -50 °C, et qui présente une grande fiabilité de cycle froid/chaleur.　L'invention concerne un film contenant une résine liante (SA) et une charge thermoconductrice (SD) dans lequel la charge thermoconductrice (SD) contenant une première charge thermoconductrice (SD1) et une seconde charge thermoconductrice (SD2) ; le diamètre moyen de particule primaire de la première charge thermoconductrice (SD1) est de 1,0 à 200 µm ; le diamètre moyen de particule primaire de la seconde charge thermoconductrice (SD2) est supérieur ou égal à 0,010 µm et inférieur à 1,0 µm ; la contrainte de cisaillement à -50 °C est de 0,70 à 20 ; et la conductivité thermique à 25 °C est de 0,10 à 5,0 W/ (m·k).
PCT/JP2023/032488 2022-09-21 2023-09-06 Film, stratifié, appareil de traitement au plasma et procédé de fabrication de stratifié Ceased WO2024062923A1 (fr)

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JP2023555260A JPWO2024062923A1 (fr) 2022-09-21 2023-09-06
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WO2013065758A1 (fr) * 2011-11-02 2013-05-10 日立化成株式会社 Composition de résine, et feuille de résine, préimprégné, laminé, substrat métallique, carte de circuit imprimé et dispositif semi-conducteur de puissance utilisant ceux-ci
JP2018053092A (ja) * 2016-09-28 2018-04-05 味の素株式会社 樹脂組成物
WO2021079900A1 (fr) * 2019-10-25 2021-04-29 パナソニックＩｐマネジメント株式会社 Composition de résine, film de résine, film métallique attaché à la résine, préimprégné, feuille stratifiée à plaquage métallique, et carte de câblage imprimée
JP2021091783A (ja) * 2019-12-10 2021-06-17 東レ株式会社 組成物、硬化物、多層シート、放熱部品、並びに電子部品
JP2021091784A (ja) * 2019-12-10 2021-06-17 東レ株式会社 硬化物、多層シート、放熱部品、並びに電子部品
WO2023068044A1 (fr) * 2021-10-19 2023-04-27 東レ株式会社 Composition de résine, produit durci à partir de celle-ci, stratifié l'utilisant, mandrin électrostatique et dispositif de traitement au plasma

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JP5422413B2 (ja) 2010-01-25 2014-02-19 電気化学工業株式会社 放熱部材及びその製造方法
JP6250949B2 (ja) 2013-04-15 2017-12-20 日本特殊陶業株式会社 半導体製造装置用部品及びその製造方法
JP6621882B2 (ja) 2018-08-08 2019-12-18 東京エレクトロン株式会社 エッチング装置

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WO2012046814A1 (fr) * 2010-10-06 2012-04-12 日立化成工業株式会社 Feuille de résine multicouche et procédé de production de cette dernière, stratifié de feuille de résine et procédé de production de ce dernier, feuille de résine multicouche durcie, feuille de résine multicouche plaquée sur une feuille de métal et dispositif à semi-conducteurs
WO2013065758A1 (fr) * 2011-11-02 2013-05-10 日立化成株式会社 Composition de résine, et feuille de résine, préimprégné, laminé, substrat métallique, carte de circuit imprimé et dispositif semi-conducteur de puissance utilisant ceux-ci
JP2018053092A (ja) * 2016-09-28 2018-04-05 味の素株式会社 樹脂組成物
WO2021079900A1 (fr) * 2019-10-25 2021-04-29 パナソニックＩｐマネジメント株式会社 Composition de résine, film de résine, film métallique attaché à la résine, préimprégné, feuille stratifiée à plaquage métallique, et carte de câblage imprimée
JP2021091783A (ja) * 2019-12-10 2021-06-17 東レ株式会社 組成物、硬化物、多層シート、放熱部品、並びに電子部品
JP2021091784A (ja) * 2019-12-10 2021-06-17 東レ株式会社 硬化物、多層シート、放熱部品、並びに電子部品
WO2023068044A1 (fr) * 2021-10-19 2023-04-27 東レ株式会社 Composition de résine, produit durci à partir de celle-ci, stratifié l'utilisant, mandrin électrostatique et dispositif de traitement au plasma

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