Film, laminate, plasma processing apparatus, and manufacturing method of laminate

Abstract

The present invention addresses the problem of providing a film that has excellent adhesion for bonding members, even at an extremely low temperature of about -50°C, and has high cold / heat cycle reliability.　The invention relates to a film containing a binder resin (SA) and a heat conductive filler (SD), wherein: the heat conductive filler (SD) contains a first heat conductive filler (SD1) and a second heat conductive filler (SD2); the average primary particle diameter of the first heat conductive filler (SD1) is 1.0-200 μm; the average primary particle diameter of the second heat conductive filler (SD2) is 0.010 μm or more and less than 1.0 μm; the shear strain at -50°C is 0.70-20; and the heat conductivity at 25°C is 0.10-5.0 W / (m·K).

Description

Film, laminate, plasma treatment apparatus, and method for manufacturing laminate

[0001] The present invention relates to a film, a laminate, a plasma processing apparatus, and a method for manufacturing a laminate.

[0002] In recent years, electronic terminal devices have become more functional, smaller, thinner, and lighter. These electronic terminal devices are equipped with semiconductor devices, such as processors and memories. In the semiconductor manufacturing process, coating liquids such as adhesives and adhesive sheets are used for the purpose of joining components together and temporarily holding components during the manufacturing process.

[0003] Electrostatic chucks are used to attract and hold semiconductor wafers, glass substrates, and other substrates in substrate processing equipment used in semiconductor manufacturing processes, such as sputtering, deposition, chemical vapor deposition, ion implantation, etching, ashing, exposure, and inspection. For example, plasma processing equipment has a mounting table for placing a semiconductor wafer inside a vacuum chamber. The mounting table primarily consists of an electrostatic chuck and a cooler for controlling the temperature of the electrostatic chuck. An electrostatic chuck is fabricated by sandwiching an electrode between ceramic dielectric members and firing them. It includes a base member, a ceramic dielectric member made of ceramic, and an adhesive member for bonding the base member and the ceramic dielectric member. An electrostatic chuck is a holding device that attracts and holds a semiconductor wafer or other substrate on the surface of a ceramic dielectric member by using electrostatic attraction generated by applying a voltage to the built-in electrode.

[0004] Meanwhile, in the manufacture of semiconductor devices, etching processes with a high aspect ratio that increase the etching depth are required to achieve higher density and higher integration in devices such as 3D-NAND memories. To improve the aspect ratio and reduce the process time in the etching process, methods of etching at extremely low temperatures of -30°C or lower (see, for example, Patent Document 1) are known. Therefore, there is a demand for adhesive members that can be used at extremely low temperatures of -30°C or lower. Such adhesive members that can be used at extremely low temperatures are also needed in other holding devices, such as vacuum chucks, in addition to electrostatic chucks.

[0005] Examples of adhesive members used in electrostatic chucks and the like include silicone resin adhesive members and acrylic resin adhesive members (see, for example, Patent Document 2 or Patent Document 3).

[0006] Japanese Patent No. 6621882 Japanese Patent Application Laid-Open No. 2011-151280 Japanese Patent Application Laid-Open No. 2014-207374

[0007] However, the adhesive members described in Patent Document 2 and Patent Document 3 have problems such as a decrease in mechanical properties at extremely low temperatures of −30° C. or below, resulting in a decrease in adhesion between members, which can lead to peeling of the members and the occurrence of cracks in the adhesive member. 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.

[0008] In order to solve the above-mentioned problems, the film of the present invention has the following constitutions [1] to

[20] .

[0009] [1] A film containing (SA) a binder resin and (SD) a thermally conductive filler, wherein the (SD) thermally conductive filler comprises (SD1) a first thermally conductive filler and (SD2) a second thermally conductive filler, wherein the (SD1) first thermally conductive filler has an average primary particle size of 1.0 to 200 μm, and the (SD2) second thermally conductive filler has an average primary particle size of 0.010 μm or more and less than 1.0 μm, wherein the film has a shear strain at −50°C of 0.70 to 20, and a thermal conductivity at 25°C of 0.10 to 5.0 W / (m·K).

[0010] [2] The film according to [1] above, having an elastic modulus at -50°C of 0.10 to 200 MPa.

[0011] [3] The film according to [1] or [2] above, which satisfies at least one of the following conditions (S1a), (S2a), (S3a), (S1b), (S2b), and (S3b): (S1a) the content of boron element in the film is 5.0 mass% or less, (S2a) the content of phosphorus element in the film is 1,000 mass ppm or less, (S3a) the total content of chlorine element and bromine element in the film is 1,000 mass ppm or less, (S1b) 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 5,000 mass ppm or less, and (S3b) the total content of chloride ion and bromide ion in the film is 1,000 mass ppm or less.

[0012] [4] The film according to any one of [1] to [3] above, which satisfies at least one of the following conditions (S4a) and (S4b): (S4a) The content of platinum element in the film is 1,000 ppm by mass or less, and (S4b) The total content of ions including platinum element in the film is 5,000 ppm by mass or less.

[0013] [5] The film according to any one of [1] to [4] above, 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 ppm by mass or less, and (S5b) the total content of cyclic silicone compounds in the film is 1,000 ppm by mass or less.

[0014] [6] A film containing (SA) a binder resin and (SD) a thermally conductive filler, the film having an elastic modulus of 0.10 to 200 MPa at -50°C and a thermal conductivity of 0.10 to 5.0 W / (m·K) at 25°C.

[0015] [7] The film according to [6] above, having a shear strain of 0.70 to 20 at -50°C.

[0016] [8] The film according to [6] or [7] above, which satisfies at least one of the following conditions (S1a), (S2a), (S3a), (S1b), (S2b), and (S3b): (S1a) the content of boron in the film is 5.0 mass% or less, (S2a) the content of phosphorus in the film is 1,000 mass ppm or less, (S3a) the total content of chlorine and bromine in the film is 1,000 mass ppm or less, (S1b) the total content of ions containing boron in the film is 5.0 mass% or less, (S2b) the total content of ions containing phosphorus in the film is 5,000 mass ppm or less, and (S3b) the total content of chloride ions and bromide ions in the film is 1,000 mass ppm or less.

[0017] [9] The film according to any one of [6] to [8] above, which satisfies at least one of the following conditions (S4a) and (S4b): (S4a) The content of platinum element in the film is 1,000 ppm by mass or less, and (S4b) The total content of ions including platinum element in the film is 5,000 ppm by mass or less.

[0018]

[10] The film according to any one of [6] to [9] above, 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 ppm by mass or less, and (S5b) the total content of cyclic silicone compounds in the film is 1,000 ppm by mass or less.

[0019]

[11] The film according to any one of [1] to

[10] , wherein the binder resin (SA) contains a resin containing a silicone structure and / or a siloxane structure in the structural unit of the resin (SA1).

[0020]

[12] The film according to

[11] , wherein the content ratio of the aliphatic groups to the total of the aliphatic groups and aromatic groups bonded to silicon atoms in the silicone structure and / or the siloxane structure is 80 to 100 mol %.

[0021]

[13] The film according to

[11] or

[12] , wherein the resin containing a silicone structure and / or a siloxane structure in the structural unit of the (SA1) resin contains a resin containing one or more structures selected from the group consisting of an imide structure, an amide structure, and an oxazole structure in the structural unit of the (SA1-1) resin.

[0022]

[14] The film according to

[13] above, wherein the resin (SA1-1) containing one or more selected from the group consisting of an imide structure, an amide structure, and an oxazole structure in its structural unit has one or more selected from the group consisting of residues of the following (1) and (2): (1) a diamine residue, a diamine derivative residue, a bisaminophenol compound residue, or a bisaminophenol compound derivative residue, each containing a silicone structure and / or a siloxane structure, or (2) a tetracarboxylic acid residue, a tetracarboxylic acid derivative residue, a tricarboxylic acid residue, a tricarboxylic acid derivative residue, a dicarboxylic acid residue, or a dicarboxylic acid derivative residue, each containing a silicone structure and / or a siloxane structure.

[0023]

[15] The film according to any one of [1] to

[14] above, which contains (SB) an epoxy compound or a compound having a structure derived from an epoxy compound (hereinafter referred to as "(SB) compound"), wherein the (SB) compound contains one or more compounds selected from the group consisting of (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 (SB3) a compound having a tertiary amine structure bonded to an arylene group and two divalent organic groups.

[0024]

[16] The film according to any one of the above [1] to

[15] , which contains (SC) an amine compound or a compound having a structure derived from an amine compound (hereinafter referred to as "(SC) compound"), and 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.

[0025]

[17] The film according to any one of [1] to

[16] , wherein the elastic modulus of the film at 25°C is 0.010 to 1.0 MPa.

[0026]

[18] The film according to any one of [1] to

[16] , wherein the film is a cured product of a composition.

[0027]

[19] The film according to any one of [1] to

[18] above, which is used in an electrostatic chuck.

[0028]

[20] A laminate having a base member, the film according to any one of [1] to

[19] , and a ceramic dielectric member in this order, wherein the base member and the ceramic dielectric member have different thermal expansion coefficients.

[0029]

[21] The laminate according to

[20] , wherein the difference in thermal expansion coefficient between the base member and the ceramic dielectric member is 1.0 to 30 ppm / K.

[0030]

[22] A plasma processing apparatus comprising a plasma generation source and the laminate according to

[20] or

[21] .

[0031]

[23] 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] ; ​​and arranging a ceramic dielectric member.

[0032] According to the present invention, it is possible to provide a film that has excellent adhesion for bonding members together even at extremely low temperatures of about -50°C and has high thermal cycle reliability.

[0033] 1A and 1B are schematic cross-sectional views showing a first embodiment of a laminate, which is a laminate having a first support, a film, and a second support, and a second embodiment of a laminate, which is a laminate having a base member, a film, and a ceramic dielectric member.

[0034] The film of the present invention will be described below. When referring to the film of the present invention, this description is common to both the first and second embodiments of the film of the present invention. On the other hand, when referring to a film of a specific embodiment, it will be referred to as the first embodiment of the film of the present invention. However, the present invention is not limited to the following embodiments, and various modifications are naturally possible within the scope of the invention, as long as the object of the invention can be achieved and the gist of the invention is not deviated from.

[0035] The main chain of a resin refers to the longest chain among the chains constituting the resin containing structural units. The side chain of a resin refers to a chain branched from or bonded to the main chain among the chains constituting the resin containing structural units, which is shorter than the main chain. The term "terminal end of a resin" refers to a structure that blocks the main chain, such as a structure derived from a terminal blocking agent.

[0036] In this specification, "overlapping" refers to directly or indirectly overlapping with respect to the z-axis direction. That is, when a layer overlaps another layer, the layers may be in contact with each other, or another layer may be present between the layers.

[0037] In this specification, a silicone structure refers to a structure having an Si-O-Si bond as the main backbone and two organic groups on the silicon atom. That is, the silicon atom in the silicone structure is bonded to two organic groups and two oxygen atoms. Furthermore, a siloxane structure refers to a structure having an Si-O-Si bond as the main backbone and one organic group on the silicon atom. That is, the silicon atom in the siloxane structure is bonded to one organic group and three oxygen atoms.

[0038] <Film> A first aspect of the film of the present invention is a film containing (SA) a binder resin and (SD) a thermally conductive filler, wherein the (SD) thermally conductive filler comprises (SD1) a first thermally conductive filler and (SD2) a second thermally conductive filler, the first thermally conductive filler (SD1) having an average primary particle diameter of 1.0 to 200 μm, the second thermally conductive filler (SD2) having an average primary particle diameter of 0.010 μm or more and less than 1.0 μm, a shear strain at −50° C. of 0.70 to 20, and a thermal conductivity at 25° C. of 0.10 to 5.0 W / (m·K). By adopting the above-mentioned configuration, the present invention can provide a film that has excellent adhesion for joining members together even at extremely low temperatures of about −50° C. and high thermal cycle reliability. This is thought to be because the anchoring effect of the combined use of a filler with a specific average primary particle size reduces the slope of the stress-strain curve, with stress on the vertical axis and strain on the horizontal axis (increasing strain per unit stress), making it possible to adjust the shear strain at -50°C within a specific range. Therefore, due to the high shear strain at extremely low temperatures of around -50°C, the film has flexibility that can alleviate the difference in thermal expansion coefficient between the members it joins, improving its ability to conform to each member, and it is presumed that this improves adhesion and thermal cycle reliability.

[0039] It is also believed that the film's inclusion of two types of thermally conductive fillers with specific average primary particle sizes allows for efficient dissipation of heat generated in the components being joined, reducing internal stress caused by temperature rises in the components. It is also believed that this reduces the heat stored in the film, suppressing changes in mechanical properties due to temperature rises in the film.

[0040] It is also thought that the high thermal conductivity of the film allows for efficient dissipation of heat generated in the joining components, reducing internal stress caused by temperature rises in the components. In addition, it is thought that the heat stored in the film can be reduced, suppressing changes in mechanical properties due to temperature rises in the film.

[0041] The term "film" refers to a film that can be formed into a free-standing film by itself. The film preferably has adhesive properties, and is also preferably formed by joining multiple components. The term "free-standing film" refers to a film that can be formed into a free-standing film by itself 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 μm or more.

[0042] A second embodiment of the film of the present invention is a film containing (SA) a binder resin and (SD) a thermally conductive filler, wherein the film has an elastic modulus at −50° C. of 0.10 to 200 MPa and a thermal conductivity at 25° C. of 0.10 to 5.0 W / (m K).

[0043] By adopting the above-described configuration, the present invention can provide a film that has excellent adhesion for bonding members together even at extremely low temperatures of about −50° C. and high thermal cycle reliability. This is presumably because the low elastic modulus at extremely low temperatures of about −50° C. reduces internal stress caused by the difference in thermal expansion coefficient between the members to which the film is bonded, improving conformity to each member, thereby improving adhesion and thermal cycle reliability.

[0044] It is also thought that the high thermal conductivity of the film allows for efficient dissipation of heat generated in the joining components, reducing internal stress caused by temperature rises in the components. In addition, it is speculated that the heat stored in the film can be reduced, suppressing changes in mechanical properties due to temperature rises in the film.

[0045] <(SA) Binder Resin> The film of the present invention contains a (SA) binder resin. The (SA) binder resin is a heat-resistant resin, at least a portion of which remains in a 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 a reaction, and may be formed by heating, irradiation with energy rays, or the like, but is not particularly limited thereto.

[0046] The binder resin (SA) 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 a repeating unit of the resin. The acidic group is preferably a phenolic hydroxyl group, a hydroxyimide group, a hydroxyamide group, a silanol group, a 1,1-bis(trifluoromethyl)methylol group, a mercapto group, a carboxy group, a carboxylic acid anhydride group, or a sulfonic acid group, and more preferably a phenolic hydroxyl group, a carboxy group, or a carboxylic acid anhydride group. Note that when the binder resin (SA) satisfies the following conditions (P1a) and / or (P2a) described below, or when the film of the present invention satisfies at least one of the following conditions (S3α) and (S3β) described below, 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.

[0047] 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 thermal cycle reliability, while the acid equivalent of the (SA) binder resin is preferably 600 g / mol or less, more preferably 500 g / mol or less, and even more preferably 450 g / mol or less from the viewpoint of improving thermal cycle reliability.

[0048] The binder resin (SA) having the above-mentioned acidic group or a structure derived from an acidic group is suitable for adjusting the shear strain at -50°C to within a range of 0.70 to 20 and / or adjusting the modulus of elasticity at -50°C to within a range of 0.10 to 200 MPa by forming a crosslinked structure with the compound (SB) described below. Furthermore, the acidic group or the structure derived from an acidic group can improve the dispersibility of the thermally conductive filler (SD) described below through interaction, resulting in a significant improvement in the thermal conductivity of the film. These factors are thought to improve conformability to each component, thereby improving adhesion and thermal cycle reliability.

[0049] <(SA1) Resin> From the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability, the (SA) binder resin preferably contains a resin containing a silicone structure and / or a siloxane structure in the structural unit of the (SA1) resin (hereinafter referred to as “(SA1) resin”).

[0050] The silicone structure and siloxane structure of the (SA1) resin are bonded to at least two alkylene groups, and are preferably divalent or higher structures via these alkylene groups. The divalent or higher structures are more preferably trivalent or higher, and even more preferably tetravalent or higher. On the other hand, the divalent or higher structures are preferably hexavalent or lower.

[0051] The number of silicon atoms contained in the silicone structure and / or siloxane structure in the (SA1) 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.

[0052] In the (SA1) resin, the silicone structure is preferably a dialkylsilicone structure and / or a monoalkylsilicone structure, and the siloxane structure is preferably a monoalkylsiloxane structure.

[0053] The number of carbon atoms in the alkyl group of the dialkyl silicone structure and monoalkyl silicone structure is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. On the other hand, 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.

[0054] 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. On the other hand, 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.

[0055] In the (SA1) resin, the content ratio of the aliphatic groups to the total of the aliphatic groups and aromatic groups bonded to silicon atoms in the silicone structure and / or siloxane structure is preferably 80 mol% or more, more preferably 85 mol% or more, and even more preferably 90 mol% or more, from the viewpoint of improving adhesion and thermal cycle reliability. On the other hand, the content ratio of the aliphatic groups to the total of the aliphatic groups and aromatic groups 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 thermal cycle reliability.

[0056] The aliphatic group contained in the (SA1) resin is preferably an alkyl group. The preferred number of carbon atoms in the alkyl group is the same as above. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group. The number of carbon atoms in the aromatic group contained in the (SA1) 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, a tolyl group, a xylyl group, a phenoxy group, a tolyloxy group, or a xylyloxy group.

[0057] The (SA1) resin as described above is suitable for adjusting the shear strain at −50° C. to within a range of 0.70 to 20 and / or adjusting the elastic modulus at −50° C. to within a range of 0.10 to 200 MPa due to the flexible skeleton derived from the silicone structure or siloxane structure.

[0058] <(SA1-1) Resin> From the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability, the (SA1) resin preferably contains a resin containing one or more structures selected from the group consisting of an imide structure, an amide structure, and an oxazole structure in the structural unit of the (SA1-1) resin (hereinafter referred to as the (SA1-1) resin).

[0059] The (SA1-1) resin is a resin containing one or more structures selected from the group consisting of an imide structure, an amide structure, and an oxazole structure in its structural unit, such as polyimide, polybenzoxazole, precursors thereof, and copolymers of two or more of them.

[0060] From the viewpoint of improving adhesion and thermal cycle reliability, the (SA1-1) resin preferably contains one or more resins selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, polyamide, and copolymers of two or more of them (hereinafter referred to as "polyimide resins"). The (SA1-1) resin may be either a single resin or a copolymer thereof.

[0061] The (SA1-1) resin preferably has one or more residues selected from the group consisting of the following residues (1) and (2): (1) a diamine residue, a diamine derivative residue, a bisaminophenol compound residue, or a bisaminophenol compound derivative residue, each containing a silicone structure and / or a siloxane structure; and (2) a tetracarboxylic acid residue, a tetracarboxylic acid derivative residue, a tricarboxylic acid residue, a tricarboxylic acid derivative residue, a dicarboxylic acid residue, or a dicarboxylic acid derivative residue, each containing a silicone structure and / or a siloxane structure.

[0062] The residue (1) contained in the (SA1-1) resin 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 bisaminophenol compound residue containing a silicone structure and / or a siloxane structure, or a bisaminophenol compound derivative residue containing a silicone structure and / or a siloxane structure.

[0063] The residue (2) contained in the (SA1-1) resin 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 dicarboxylic acid derivative residue containing a silicone structure and / or a siloxane structure.

[0064] The residue of (1) contained in the resin (SA1-1) is divalent or higher, preferably trivalent or higher. On the other hand, the residue of (1) is preferably hexavalent or lower, more preferably tetravalent or lower. Furthermore, the residue of (2) contained in the resin (SA1-1) is divalent or higher, preferably trivalent or higher, more preferably tetravalent or higher. On the other hand, the residue of (2) is preferably hexavalent or lower.

[0065] The residue (2) contained in the resin (SA1-1) is preferably a tetracarboxylic dianhydride residue, a tricarboxylic anhydride residue, or a dicarboxylic anhydride residue containing a silicone structure and / or a siloxane structure, and the residue (2) is preferably 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.

[0066] In the (SA1-1) resin, the total content of the residues (1) and (2) in the total of all amine residues and all carboxylic acid residues 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, from the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability. On the other hand, the total content of the residues (1) and (2) in the total of all amine residues and 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 thermal cycle reliability.

[0067] In the (SA1-1) resin, the total content of the residues of (1) in all amine residues 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, from the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability. On the other hand, the total content of the residues of (1) 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 thermal cycle reliability.

[0068] In the (SA1-1) resin, the total content of the residues of (2) in all carboxylic acid residues 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, from the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability. On the other hand, the total content of the residues of (2) 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 thermal cycle reliability.

[0069] The residue (1) in the resin (SA1-1) preferably has a structure represented by general formula (11). The residue (2) in the resin (SA1-1) preferably has a structure represented by general formula (12).

[0070]

[0071] In the general formula (11) and the general formula (12), X １ ~X ４ each independently represents 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. １ and Y ２ R each independently represents a trivalent organic group having 1 to 20 carbon atoms. ２１ ~R ３２ each independently represents 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 ~* ８ each independently represents a point of attachment to another structure.

[0072] In general formula (11) and general formula (12), 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, 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 alkylene group have a linear or branched structure. The above alkyl group, aryl group, aryloxy group, alkylene group and arylene group may contain a heteroatom and may be unsubstituted or substituted.

[0073] From the viewpoints of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability, x is preferably 6 or more, more preferably 15 or more, even more preferably 24 or more, still more preferably 28 or more, and particularly preferably 32 or more. On the other hand, from the viewpoints of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability, x is preferably 100 or less, more preferably 70 or less, even more preferably 50 or less, and particularly preferably 44 or less.

[0074] From the viewpoints of improving adhesion at extremely low temperatures of about −50° C. and improving reliability in thermal cycles, y is preferably 6 or more, more preferably 11 or more, even more preferably 15 or more, and particularly preferably 18 or more. On the other hand, from the viewpoints of improving adhesion at extremely low temperatures of about −50° C. and improving reliability in thermal cycles, y is preferably 100 or less, more preferably 50 or less, even more preferably 30 or less, and particularly preferably 26 or less.

[0075] In resin (SA1-1), the total content of structures represented by general formula (11) in which x is 6 or more and 100 or less in the residue of (1) is preferably 50 mol % or more, more preferably 70 mol % or more, and even more preferably 90 mol % or more, from the viewpoint of the effects of the invention. On the other hand, the total content of structures represented by general formula (11) in which x is 6 or more and 100 or less is preferably 100 mol % or less, more preferably 99 mol % or less, and even more preferably 97 mol % or less, from the viewpoint of the effects of the invention.

[0076] In resin (SA1-1), the total content of structures represented by general formula (12) in which y is 6 or more and 100 or less in the residue of (2) is preferably 50 mol % or more, more preferably 70 mol % or more, and even more preferably 90 mol % or more, from the viewpoint of the effects of the invention described above. On the other hand, the total content of structures represented by general formula (12) in which y is 6 or more and 100 or less is preferably 100 mol % or less, more preferably 99 mol % or less, and even more preferably 97 mol % or less, from the viewpoint of the effects of the invention described above.

[0077] The (SA1-1) resin described above is suitable for adjusting the shear strain at −50° C. to within a range of 0.70 to 20 and / or adjusting the elastic modulus at −50° C. to within a range of 0.10 to 200 MPa due to the improved mechanical properties of the imide structure, amide structure, or oxazole structure in addition to the flexible backbone derived from the silicone structure or siloxane structure. Furthermore, the (SA1-1) resin is believed to function as an anchor at the interface with components at extremely low temperatures due to the coordination ability with each component derived from the imide structure, amide structure, or oxazole structure. Therefore, it is estimated that the conformability to each component is improved, and the adhesion and thermal cycle reliability are improved.

[0078] Examples of the amine monomer for introducing the residue (1) into the (SA1-1) resin include dimethyl silicones modified with amino groups at both ends, such as 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), and KF-8008 (amino group equivalent: 5,700 g / mol) (all manufactured by Shin-Etsu Chemical Co., Ltd.), and methyl phenyl silicones modified with amino groups at both ends, such as X-22-1660B-3 (amino group equivalent: 2,200 g / mol) and X-22-9409 (amino group equivalent: 650 g / mol) (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0079] Examples of the acid monomer for introducing the residue (2) into the resin (SA1-1) 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), and X-22-168-P5-B (acid anhydride group equivalent: 2,100 g / mol) (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0080] The (SA1-1) resin preferably has a residue having an acidic group or a residue having a structure derived from an acidic group, and more preferably has a residue having an acidic group or a residue having a structure derived from an acidic group in a repeating unit of the resin. Examples of amine monomers or acid monomers for introducing such residues into the (SA1-1) 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-amino-4-hydroxyphenyl)sulfone, bis[4-(4-aminophenoxy)phenyl]propane ... phenyl] ether, bis(3-amino-4-hydroxyphenyl) ether, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3-aminobenzoic acid amide), or N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3,4-dicarboxybenzoic acid amide).

[0081] <Polyimide Resin> Examples of polyimide precursors include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide. Examples of polyimides include resins obtained by dehydrating and ring-closing a polyimide precursor by heating or a reaction using a catalyst.

[0082] Examples of polybenzoxazole precursors include polyhydroxyamides, and examples of polybenzoxazoles include resins obtained by dehydrating and cyclizing polybenzoxazole precursors by heating or by a reaction using a catalyst.

[0083] Examples of polyamide-imide precursors include resins obtained by reacting tricarboxylic acid anhydrides with diamines, etc. Examples of polyamide-imides include resins obtained by dehydrating and ring-closing polyamide-imide precursors by heating or by a reaction using a catalyst.

[0084] Examples of polyamides include resins obtained by reacting a dicarboxylic acid or a corresponding dicarboxylic acid activated diester with a diamine or a diisocyanate compound. The above-mentioned polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor may be copolymerized with polyamide.

[0085] The polyimide resin may have a structure in which the terminals of the resin are sealed with a monoamine, a dicarboxylic anhydride, or a monocarboxylic acid derivative. From the viewpoint of improving adhesion and thermal cycle reliability, the polyimide resin preferably has a crosslinkable group or a radical polymerizable group capable of reacting with resins, etc., at the terminals of the resin, and more preferably has a maleimide group or a nadimide group.

[0086] <Fluorine Element Content in the Structure of the (SA) Binder Resin> From the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability, it is also preferable that the (SA) binder resin satisfy the following condition (P1a). It is more preferable that the (SA) binder resin further satisfy the following condition (P2a). From the same viewpoint, even when the (SA) binder resin is a polyimide-based resin, it is also preferable that the (SA) binder resin satisfy the following condition (P1a), and it is more preferable that the (SA) binder resin further satisfy the following condition (P2a). Note that when the (SA) binder resin satisfies the following condition (P2a), the following condition (P1a) is satisfied by the fluoride ions 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. (P2a) (SA) The content of fluoride ions in the structure of the binder resin is 10,000 mass ppm or less.

[0087] From the viewpoint of the effects of the present invention, the content of elemental fluorine in the structure of the (SA) binder resin is preferably more than 0.000 ppm by mass, more preferably 0.010 ppm by mass or more, even more preferably 0.030 ppm by mass or more, still more preferably 0.050 ppm by mass or more, particularly preferably 0.070 ppm by mass or more, and particularly preferably 0.10 ppm by mass or more. On the other hand, from the viewpoint of the effects of the present invention described above, the content of elemental fluorine is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, even more preferably 1,000 ppm by mass or less, still more preferably 500 ppm by mass or less, still more preferably 300 ppm by mass or less, still more preferably 100 ppm by mass or less, still more preferably 50 ppm by mass or less, still more preferably 30 ppm by mass or less, still more preferably 10 ppm by mass or less, still more preferably 5 ppm by mass or less, particularly preferably 3 ppm by mass or less, and particularly preferably 1 ppm by mass or less.

[0088] Elemental fluorine has many unshared electron pairs, and it is thought that by including elemental fluorine in the structure of the (SA) binder resin, it is easier to form coordinate bonds to the surface of the component due to electron donation using these electron pairs.

[0089] The preferred ranges of the content of fluoride ions in the structure of the (SA) binder resin are the same as the preferred ranges of the content of fluorine elements in the structure of the (SA) binder resin with respect to the upper and lower limits.

[0090] The content of fluorine element in the structure of the (SA) binder resin may be 0.000 mass ppm, and the content of fluoride ions in the structure of the (SA) binder resin may also be 0.000 mass ppm.

[0091] By incorporating a (SA) binder resin with a fluorine content below a specific value into the film, the content of fluorine elements, fluoride ions, or fluorine-containing anions derived from these resins is below a specific value. This is thought to improve local interactions with the surfaces of the components to be joined due to the hydrogen bonds of each component in the film and the electronegativity of fluorine atoms. Furthermore, intentionally setting the content of these components below a specific value is thought to control the polarization structure and charge balance in the film, thereby suppressing the effects of ionic components that adversely affect the mechanical properties of the film during thermal cycling. These actions allow the film to function as an anchor at the interface with the components at extremely low temperatures, improving conformability to each component and improving adhesion and thermal cycling reliability.

[0092] <(SA1-2) Resin> From the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability, the (SA1) resin preferably contains a (SA1-2) silicone resin and / or polysiloxane (hereinafter referred to as “(SA1-2) resin”).

[0093] Examples of resin (SA1-2) include resins obtained by hydrolyzing one or more organosilanes selected from the group consisting of bifunctional organosilanes, trifunctional organosilanes, tetrafunctional organosilanes, and monofunctional organosilanes, followed by dehydration condensation. Resin (SA1-2) may have functional groups introduced into the organic groups on the silicon atoms by hydrosilylation.

[0094] Silicone resins are resins 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, with the silicon atom bonded to two oxygen atoms. In the silicone resin, the content of the bifunctional organosilane units in the total organosilane units is 50 mol% or more, preferably 60 mol% or more, and more preferably 70 mol% or more. Meanwhile, the content of the bifunctional organosilane units is preferably 100 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol%.

[0095] Polysiloxane is a resin whose main skeleton is a structural unit containing a siloxane structure. That is, the main skeleton is a trifunctional organosilane unit having one organic group with two organic groups on a silicon atom, and the silicon atom being bonded to three oxygen atoms. In the silicone resin, the content ratio of the trifunctional organosilane unit to all organosilane units is 50 mol% or more, preferably 60 mol% or more, and more preferably 70 mol% or more. Meanwhile, 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%.

[0096] The (SA1-2) resin preferably contains one or more units selected from the group consisting of the following units (3) and (4): (3) a difunctional organosilane unit, trifunctional organosilane unit, tetrafunctional organosilane unit, or monofunctional organosilane unit having an aliphatic group, and (4) a difunctional organosilane unit, trifunctional organosilane unit, tetrafunctional organosilane unit, or monofunctional organosilane unit having an aromatic group.

[0097] The silicone resin preferably contains a difunctional organosilane unit having an aliphatic group and / or a difunctional organosilane unit having an aromatic group, and the polysiloxane preferably contains a trifunctional organosilane unit having an aliphatic group and / or a trifunctional organosilane unit having an aromatic group.

[0098] The aliphatic group contained in the resin (SA1-2) 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. On the other hand, 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, an ethyl group, a propyl group, a butyl group, or a hexyl group.

[0099] The number of carbon atoms in the aromatic group contained in the resin (SA1-2) 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, a tolyl group, a xylyl group, a phenoxy group, a tolyloxy group, or a xylyloxy group.

[0100] In the (SA1-2) resin, the total content of the units of (3) relative to all organosilane units is preferably 70 mol % or more, more preferably 80 mol % or more, even more preferably 85 mol % or more, and particularly preferably 90 mol % or more, from the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability. On the other hand, the total content of the units of (3) relative to all organosilane units is preferably 100 mol % or less, more preferably 99 mol % or less, even more preferably 97 mol % or less, and particularly preferably 95 mol % or less, from the viewpoint of improving thermal cycle reliability.

[0101] In the (SA1-2) resin, the total content of the units of (4) relative to all organosilane units is preferably 1.0 mol % or more, more preferably 3.0 mol % or more, and even more preferably 5.0 mol % or more, from the viewpoint of improving thermal cycle reliability. On the other hand, the total content of the units of (4) relative to 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 adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability.

[0102] The (SA1-2) resin preferably further contains the following unit (5): (5) Difunctional organosilane unit, trifunctional organosilane unit, tetrafunctional organosilane unit, or monofunctional organosilane unit having an epoxy group The (SA1-2) resin preferably contains a difunctional organosilane unit having an epoxy group and / or a trifunctional organosilane unit having an epoxy group.

[0103] In the (SA1-2) resin, the total content of the units (5) relative to all organosilane units is preferably 1.0 mol % or more, more preferably 3.0 mol % or more, and even more preferably 5.0 mol % or more, from the viewpoints of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability. On the other hand, the total content of the units (5) relative to 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 viewpoints of improving thermal cycle reliability.

[0104] The (SA1-2) resin as described above has a main skeleton that is a structural unit containing a silicone structure or a siloxane structure and has excellent flexibility, and is therefore suitable for adjusting the shear strain at −50° C. to within a range of 0.70 to 20 and / or adjusting the elastic modulus at −50° C. to within a range of 0.10 to 200 MPa.

[0105] <Other (SA) Binder Resins> The film of the present invention may contain other (SA) binder resins. The other (SA) binder resins are preferably maleimide resins, maleimide-styrene resins, maleimide-triazine resins, cardo resins, epoxy (meth)acrylate resins, acrylic resins, phenolic resins, phenol aralkyl resins, polyhydroxystyrenes, tetrafluoroethylene polymers, polyphenylene ethers, liquid crystal polymers, cycloolefin polymers, or benzocyclobutene resins. Known resins may be used as these resins. The other (SA) binder resins preferably have an acidic group or a structure derived from an acidic group, and more preferably have 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 groups are the same as those for the acidic groups contained in the (SA) binders described above.

[0106] A maleimide resin is a resin having at least two maleimide groups in at least one of the main chain, side chain, and terminal of the resin. Note that maleimide resins are different from polyimide-based resins.

[0107] Examples of maleimide-styrene resins include resins obtained by radical copolymerizing the above-mentioned maleimide resin with a styrene derivative, and resins obtained by radical copolymerization of a maleimide compound, a styrene derivative, and another copolymerization component such as a (meth)acrylic acid derivative.

[0108] Examples of maleimide-triazine resins include resins obtained by further reacting the above-mentioned maleimide resin with a compound having a triazine structure and / or an aromatic cyanate ester compound, and resins obtained by reacting a maleimide compound with a compound having a triazine structure and / or an aromatic cyanate ester compound.

[0109] Examples of maleimide-oxazine resins include resins obtained by further reacting the above-mentioned maleimide resin with a compound having a benzoxazine structure, and resins obtained by reacting a maleimide compound with a compound having a benzoxazine structure.

[0110] The total content of (SA1) resins relative to 100% by mass of the total of (SA) binder resins is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, from the viewpoints of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability. On the other hand, the total content of (SA1) resins is preferably 100% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less, from the viewpoint of improving adhesion.

[0111] The total content 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, while the total content 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.

[0112] <(SB) Epoxy Compound or Compound Having a Structure Derived from an Epoxy Compound> The film of the present invention preferably contains (SB) an 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. As described above, the (SB) compound is preferably a compound that forms or has formed a crosslinked structure with the (SA) binder resin.

[0113] The number of epoxy groups contained in the (SB) compound is preferably 2 or more, more preferably 3 or more, while the number of epoxy groups is preferably 6 or less, more preferably 4.

[0114] From the viewpoint of improving adhesion at cryogenic temperatures of about -50°C and improving thermal cycle reliability, the film of the present invention contains an (SB) compound, and the (SB) compound preferably contains one or more compounds selected from the group consisting of (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 a structure containing 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"). The (SB1) compound, the (SB2) compound, and the (SB3) compound may each have a structure derived from the above-mentioned compound. Note that the (SB1) compound is a different compound from the (SB2) compound and does not have a structure containing an aromatic structure.

[0115] The oxyalkylene group contained in the compound (SB1) is preferably divalent or higher, more preferably trivalent or higher, while the oxyalkylene group contained in the compound (SB1) is preferably hexavalent or lower, more preferably tetravalent or lower.

[0116] The number of oxyalkylene groups contained in the (SB1) compound 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 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 contained in the (SB1) compound 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.

[0117] The compound (SB1) preferably includes at least one selected from the group consisting of compounds represented by general formula (21) and compounds having a structure represented by general formula (22).

[0118]

[0119] In the general formula (21) and the general formula (22), X ５ represents an alkylene group having 1 to 30 carbon atoms. m represents an integer of 1 to 20. １ ~* ４ each independently represents a point of attachment to another structure.

[0120] In general formula (21) and general formula (22), 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 alkylene group has a linear or branched structure. The alkylene group may have a heteroatom and may be unsubstituted or substituted.

[0121] The structure containing at least two aromatic structures contained in 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 divalent or higher structure is more preferably trivalent or higher. On the other hand, the divalent or higher structure is preferably hexavalent or lower, more preferably tetravalent or lower.

[0122] The number of carbon atoms in the aromatic structure of the (SB2) compound 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 in the (SB2) compound is preferably 2 or more, and more preferably 3 or more. On the other hand, the number of aromatic structures is preferably 6 or less, and more preferably 4 or less.

[0123] The structure containing at least two aromatic structures in the compound (SB2) preferably has a group linking the at least two aromatic structures. The linking group is preferably 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, an oxyaryleneoxy group having 6 to 15 carbon atoms, an ether bond, a carbonyl group, a carboxylic acid ester bond, an amide bond, a urea bond, a urethane bond, a sulfonyl group, or a carbonate ester bond.

[0124] The number of oxyalkylene groups contained in the (SB2) compound is preferably 2 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 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 contained in the (SB2) compound 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.

[0125] The compound (SB2) preferably includes at least one selected from the group consisting of compounds represented by general formula (23) and compounds having a structure represented by general formula (24).

[0126]

[0127] In the general formula (23) and the general formula (24), X ６ and X ７ each independently represents an alkylene group having 1 to 30 carbon atoms. ６is preferably 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, an oxyaryleneoxy group having 6 to 15 carbon atoms, an ether bond, a carbonyl group, a carboxylic acid ester bond, an amide bond, a urea bond, a urethane bond, a sulfonyl group, or a carbonate ester bond. ３３ and R ３４ each independently represents 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 ring-forming group. The rings connected by the ring-forming group represent a monocyclic or condensed 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 ~* ４ each independently represents a point of attachment to another structure.

[0128] In general formula (23) and general formula (24), 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, a tolyl group, or a 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, an ethylene group, a propylene group, a butylene group, or a 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. The alkyl group and alkylene group have a linear or branched structure. The above alkyl group, cycloalkyl group, aryl group, alkoxy group, alkylene group, and cycloalkylene group may contain a heteroatom, and may be either unsubstituted or substituted.

[0129] The tertiary amine structure of the (SB3) compound is preferably a trivalent or higher structure bonded to an arylene group and two divalent organic groups via the arylene group and the two divalent organic groups. The trivalent or higher structure is preferably hexavalent or lower, more preferably tetravalent or lower.

[0130] The number of carbon atoms in the arylene group contained in the (SB3) compound 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 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 contained in the (SB3) compound is preferably 1 or more, and more preferably 2 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.

[0131] It is also preferable that the (SB3) compound has an oxyalkylene group. In an embodiment in which the (SB3) compound has an oxyalkylene group, the arylene group in the (SB3) compound is preferably an arylene group bonded to an oxyalkylene group. Furthermore, the divalent organic group in the (SB3) compound is preferably a divalent aliphatic group, more preferably an alkylene group. In an embodiment in which the (SB3) compound has an oxyalkylene group, the divalent aliphatic group in the (SB3) compound is preferably a divalent aliphatic group bonded to an oxyalkylene group.

[0132] The number of oxyalkylene groups contained in the (SB3) compound is preferably 2 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 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 contained in the (SB3) compound 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.

[0133] The (SB3) compound preferably includes at least one selected from the group consisting of compounds represented by general formula (25) and compounds having a structure represented by general formula (26).

[0134]

[0135] In the general formula (25) and the general formula (26), X ８ , X ９ , and X １０ R each independently represents an alkylene group having 1 to 30 carbon atoms. ３５ represents 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 ring-forming group. The rings connected by the ring-forming group represent a monocyclic or condensed polycyclic hydrocarbon ring. a represents an integer of 0 to 4. l, m, and n each independently represent an integer of 0 to 20. * １ ~* ６ each independently represents a point of attachment to another structure.

[0136] In general formula (25) and general formula (26), 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, a tolyl group, or a 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, an ethylene group, a propylene group, a butylene group, or a hexylene group. The alkyl group and alkylene group have a linear or 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.

[0137] The above-described (SB1), (SB2), and (SB3) compounds are suitable for adjusting the shear strain at -50°C to within a range of 0.70 to 20 and / or adjusting the modulus of elasticity at -50°C to within a range of 0.10 to 200 MPa due to the flexible skeleton derived from the oxyalkylene group. Furthermore, the (SB) compound is believed to function as an anchor at the interface with the component at extremely low temperatures due to the coordination ability to each component derived from the tertiary amine structure. Therefore, it is presumed that the conformability to each component is improved, and the adhesion and thermal cycle reliability are improved.

[0138] The total content of the (SB1), (SB2), and (SB3) compounds in the film is preferably 0.10 parts by mass or more, more preferably 0.50 parts by mass or more, even more preferably 1.0 part by mass or more, still more preferably 3.0 parts by mass or more, and particularly preferably 5.0 parts by mass or more, based on 100 parts by mass of the binder resin (SA). On the other hand, the total content of the (SB1), (SB2), and (SB3) compounds in the film is preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

[0139] <(SC) Amine Compound or Compound Having a Structure Derived from an Amine Compound> 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 a composition for forming the film of the present invention. The (SC) compound is preferably a compound that forms a crosslinked structure with the above-mentioned (SB) compound, or a compound that has formed a crosslinked structure. The crosslinked structure is preferably formed by a reaction, and is not particularly limited, and may be formed by heating, irradiation with energy rays, or the like.

[0140] The number of amino groups contained in the (SC) compound is preferably 2 or more, more preferably 3 or more, while the number of amino groups is preferably 6 or less, more preferably 4.

[0141] From the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability, the film of the present invention contains an (SC) compound, and the (SC) compound preferably 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 siloxane structure (hereinafter referred to as "(SC1) compound"). The (SC1) compound may be a compound having a structure derived from the above compound.

[0142] The silicone structure and siloxane structure of the (SC1) compound are bonded to at least two alkylene groups, and are preferably divalent or higher structures via these alkylene groups. The divalent or higher structures are more preferably trivalent or higher. On the other hand, the divalent or higher structures are preferably hexavalent or lower, more preferably tetravalent or lower.

[0143] The number of silicon atoms contained 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. On the other hand, the number of silicon atoms contained in the (SC1) compound is preferably 30 or less, more preferably 27 or less, and even more preferably 25 or less.

[0144] The silicone structure in the (SC1) compound is preferably a dialkyl silicone structure and / or a monoalkyl silicone structure. The number of carbon atoms in the alkyl group of the dialkyl silicone structure and the monoalkyl silicone structure is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. On the other hand, 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.

[0145] The siloxane structure in the (SC1) compound 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. On the other hand, 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.

[0146] In the (SC1) compound, the content ratio of the aliphatic groups in the total of the aliphatic groups and aromatic groups bonded to silicon atoms in the silicone structure and siloxane structure is preferably 80 mol% or more, more preferably 85 mol% or more, and even more preferably 90 mol% or more. On the other hand, from the viewpoint of improving thermal cycle reliability, the content ratio of the aliphatic groups in the total of the aliphatic groups and aromatic groups is preferably 100 mol% or less, more preferably 99 mol% or less, and even more preferably 97 mol% or less.

[0147] The aliphatic group contained in the (SC1) compound is preferably an alkyl group. The preferred number of carbon atoms in the alkyl group is the same as above. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group. The number of carbon atoms in the aromatic group contained in the (SC1) compound 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, a tolyl group, a xylyl group, a phenoxy group, a tolyloxy group, or a xylyloxy group.

[0148] The (SC1) compound preferably includes at least one selected from the group consisting of compounds represented by general formula (31) and compounds having a structure represented by general formula (32).

[0149]

[0150] In the general formula (31) and the general formula (32), X １１ and X １２ R each independently represents 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. ４１ ~R ４６ each independently represents 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 of 1 to 100. １ ~* ４ each independently represents a point of attachment to another structure.

[0151] In general formula (31) and general formula (32), 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, 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 alkylene group have a linear or 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.

[0152] The (SC1) compound as described above is suitable for adjusting the shear strain at −50° C. to within a range of 0.70 to 20 and / or adjusting the elastic modulus at −50° C. to within a range of 0.10 to 200 MPa due to the flexible skeleton derived from the silicone structure and / or siloxane structure.

[0153] 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, based on 100 parts by mass of the total of the (SA) binder resin, the (SB) compound, and the (SC) compound, while the content of the (SC1) compound in the film is preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

[0154] <(SD) Thermally Conductive Filler> The film of the present invention contains a (SD) thermally conductive filler. The (SD) thermally 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 measuring a sintered body having a thickness of approximately 1.0 mm and a porosity of 10% by volume or less in accordance with JIS R1611 (2010). While JIS R1611 (2010) states in "7.2 Measurement Methods" that "c) Bulk Density: Thermal Diffusivity is measured according to JIS R1634, etc.", in the present invention, "c) Bulk Density" refers to a value measured according to JIS R1634 (1998).

[0155] The shape of the (SD) thermally conductive filler may be, for example, spherical, globular, scaly, flake-like, foil-like, fibrous, or needle-like. From the viewpoint of improving the thermal conductivity of the film by high-density filling of the filler, spherical (SD) thermally conductive fillers are preferred.

[0156] The thermal conductivity of the (SD) thermally conductive filler at 25°C is preferably 2.0 W / (m·K) or more, more preferably 5.0 W / (m·K) or more, even more preferably 10 W / (m·K) or more, even more preferably 20 W / (m·K) or more, particularly preferably 30 W / (m·K) or more, and particularly preferably 40 W / (m·K) or more, from the viewpoint of improving adhesion and thermal cycle reliability. On the other hand, 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, even more preferably 150 W / (m·K) or less, and particularly preferably 100 W / (m·K) or less, from the viewpoint of improving thermal cycle reliability.

[0157] From the viewpoint of improving adhesion and thermal cycle reliability, the (SD) thermally conductive filler preferably contains aluminum, boron, silicon, magnesium, zinc, titanium, zirconium, yttrium, or iron as a main component element, and more preferably contains aluminum, boron, silicon, magnesium, or zinc as a main component element. The main component element refers to the element that is contained in the largest amount by mass in the constituent components.

[0158] The (SD) thermally conductive filler preferably contains one or more particles selected from the group consisting of 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, titanium carbide particles, titanium nitride particles, titanium oxide particles, zirconium oxide particles, yttrium oxide particles, and iron oxide particles.

[0159] The above-described (SD) thermally conductive filler, due to its robust structure and high thermal conductivity, is suitable for adjusting the thermal conductivity of the film at 25°C to within the range of 0.10 to 5.0 W / (m K) while maintaining the mechanical properties of the film.

[0160] In a first aspect of the film of the present invention, the thermally conductive filler (SD) comprises a first thermally conductive filler (SD1) and a second thermally conductive filler (SD2), the first thermally conductive filler (SD1) has an average primary particle size of 1.0 to 200 μm, and the second thermally conductive filler (SD2) has an average primary particle size of 0.010 μm or more and less than 1.0 μm.

[0161] In a second aspect of the film of the present invention, from the viewpoint of improving adhesion and improving thermal cycle reliability, the thermally conductive filler (SD) preferably includes a first thermally conductive filler (SD1) and a second thermally conductive filler (SD2), and it is more preferable that the average primary particle diameter of the first thermally conductive filler (SD1) is 1.0 to 200 μm, and the average primary particle diameter of the second thermally conductive filler (SD2) is 0.010 μm or more and less than 1.0 μm.

[0162] The average primary particle size of the first thermally conductive filler (SD1) is preferably 2.0 μm or more, and more preferably 3.0 μm or more, from the viewpoint of high-density packing of the filler and clarity of the filler interface.

[0163] With the above-mentioned structure, the gaps between the large particle size fillers are filled with the small particle size fillers, and the high density of the fillers significantly improves the thermal conductivity of the film. Furthermore, the efficient heat dissipation reduces the internal stress caused by the temperature rise of the components, and the film conforms to each component better, which is presumed to improve adhesion and thermal cycle reliability.

[0164] The average primary particle diameter of the first thermally conductive filler (SD1) is preferably 5.0 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, even more preferably 20 μm or more, particularly preferably 25 μm or more, and particularly preferably 30 μm or more, from the viewpoint of improving thermal cycle reliability. On the other hand, from the viewpoint of improving adhesion, the average primary particle diameter is preferably 150 μm or less, more preferably 100 μm or less, and even more preferably 80 μm or less. Furthermore, from the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability, it is preferably 60 μm or less, more preferably 50 μm or less, even more preferably 45 μm or less, and particularly preferably 40 μm or less.

[0165] The average primary particle size of the second thermally conductive filler (SD2) is preferably 0.050 μm or more, more preferably 0.10 μm or more, even more preferably 0.15 μm or more, and particularly preferably 0.20 μm or more from the viewpoint of improving thermal cycle reliability, while the average primary particle size is preferably 0.80 μm or less, more preferably 0.60 μm or less, and even more preferably 0.40 μm or less from the viewpoint of improving adhesion.

[0166] The primary particle diameter of the (SD) 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 a film can be calculated by imaging and analyzing the cross section of the film using a transmission electron microscope (hereinafter referred to as "TEM") and measuring 30 primary particles of the filler as the average value. The average primary particle diameter of the (SD1) first thermally conductive filler is the average value measured using a TEM for 30 primary particles of the filler having a primary particle diameter of 1.0 μm or more. The average primary particle diameter of the (SD2) second thermally conductive filler is the average value measured using a TEM for 30 primary particles of the filler having a primary particle diameter of less than 1.0 μm. The elements contained in the (SD) thermally conductive filler can be detected by imaging and analyzing the 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 clarify the filler interface. The average primary particle size 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 measuring instruments include the SLD3100 manufactured by Shimadzu Corporation, the LA-920 manufactured by Horiba, Ltd., or equivalents thereof.

[0167] (SD1) The specific surface area of ​​the first thermally conductive filler is 0.023 m from the viewpoint of improving adhesion. ２ / g or more is preferable, and 0.031 m ２ / g or more is more preferable, and 0.047m ２ / g or more is more preferable, and 0.059 m ２ Further, from the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability, it is particularly preferable that the thickness is 0.080 m ２ / g or more is preferable, and 0.11m ２ / g or more is more preferable, and 0.15m ２ / g or more is more preferable, and 0.18m ２ / g or more is more preferable, and 0.20m ２ / g or more is particularly preferred, and 0.23m ２ Particularly from the viewpoint of improving adhesion at extremely low temperatures of about −50° C., it is preferable that the thickness is 0.18 m / g or more. ２ / g or more is preferable, and 0.20m ２ / g or more is more preferable, and 0.23m ２ / g or more is more preferable.

[0168] On the other hand, the specific surface area of ​​the first thermally conductive filler (SD1) is set to 5.90 m from the viewpoint of high density packing of the filler and clarification of the filler interface. ２ / g or less is preferable, and 3.00m ２ / g or less is more preferable, and 2.00m ２ Further, from the viewpoint of improving the thermal cycle reliability, it is more preferable that the tensile strength is 1.20 m / g or less. ２ / g or less is preferable, and 1.00m ２ / g or less is more preferable, and 0.80m ２ / g or less is more preferable, and 0.60m ２ / g or less is more preferable, and 0.50m ２ / g or less is particularly preferred, and 0.40m ２ Particularly from the viewpoint of improving adhesion at extremely low temperatures of about −50° C., it is preferable that the thickness is 2.00 m ２ / g or less is preferable, and 1.20m ２ / g or less is more preferable, and 1.00m ２ / g or less is more preferable, and 0.80m ２ / g or less is more preferable, and 0.60m ２ / g or less is more preferable, and 0.50m ２ / g or less is more preferable, and 0.40m ２ / g or less is particularly preferred.

[0169] With the above-described configuration, the anchor effect of the filler with a specific specific surface area reduces the slope of the stress-strain curve, with the vertical axis representing stress and the horizontal axis representing strain (increasing strain per unit stress), making it suitable for adjusting the shear strain at -50°C to within a range of 0.70 to 20. Therefore, the material has flexibility that can mitigate the difference in thermal expansion coefficient between components even at extremely low temperatures, and its ability to conform to each component is improved, which is presumed to improve adhesion and thermal cycle reliability.

[0170] (SD2) The specific surface area of ​​the second thermally conductive filler is 5.91 m from the viewpoint of improving adhesion. ２ / g or more is preferable, and 8.00m ２ / g or more is more preferable, and 12.0m ２ / g or more is more preferable, and 14.6m ２ / g or more is more preferable, and 16.1m ２ / g or more is particularly preferred, and 19.5m ２ On the other hand, the specific surface area of ​​the second thermally conductive filler (SD2) is preferably 590 m / g or more from the viewpoint of improving the thermal cycle reliability. ２ / g or less is preferable, and 120m ２ / g or less is more preferable, and 60.0m ２ / g or less is more preferable, and 50.0m ２ / g or less is more preferable, and 40.0m ２ / g or less is particularly preferred, and 30.0m ２ / g or less is particularly preferred.

[0171] By using the above-mentioned structure, the gaps between the large particle size fillers are filled with the small particle size fillers, which is thought to efficiently dissipate heat generated in the components being joined and reduce internal stress caused by temperature rise in the components.In addition, it is thought that the heat stored in the film can be reduced, which can suppress changes in mechanical properties due to temperature rise in the film.

[0172] The specific surface area of ​​the (SD) thermally conductive filler can be calculated by measuring the BET specific surface area using a gas adsorption method. First, the film is heated at 600 to 900°C to thermally decompose and / or volatilize organic components such as resins, 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). Furthermore, if the remaining (SD) thermally conductive filler is a mixture of the first thermally conductive filler (SD1) and the second thermally conductive filler (SD2), the two types of fillers can be separated using a dry or wet classifier, and the specific surface area of ​​each can be measured.

[0173] From the viewpoints of improving adhesion and improving thermal cycle reliability, the content of the first thermally conductive filler (SD1) is preferably 40 vol% or more, more preferably 50 vol% or more, and even more preferably 60 vol% or more, when the total of the first thermally conductive filler (SD1) and the second thermally conductive filler (SD2) is taken as 100 vol%. On the other hand, from the viewpoints of improving adhesion and improving thermal cycle reliability, the content of the first thermally conductive filler (SD1) is preferably 80 vol% or less, more preferably 75 vol% or less, and even more preferably 70 vol% or less.

[0174] From the viewpoints of improving adhesion and improving thermal cycle reliability, the content of the second thermally conductive filler (SD2) is preferably 20% by volume or more, more preferably 25% by volume or more, and even more preferably 30% by volume or more, when the total of the first thermally conductive filler (SD1) and the second thermally conductive filler (SD2) is taken as 100% by volume. On the other hand, from the viewpoints of improving adhesion and improving thermal cycle reliability, the content of the first thermally conductive filler (SD1) is preferably 60% by volume or less, more preferably 50% by volume or less, and even more preferably 40% by volume or less.

[0175] The film of the present invention may contain other (SD) thermally conductive fillers, such as carbon black or metal fillers such as aluminum particles, magnesium particles, silver particles, zinc particles, iron particles, or lead particles.

[0176] The content of the (SD) thermally conductive filler in the film is preferably 50% by volume or more, more preferably 60% by volume or more, and even more preferably 70% by volume or more, while the content 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.

[0177] The content of the (SD) thermally conductive filler can be calculated using a method of measurement 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, and the mass of the remaining (SD) thermally conductive filler is measured. The mass of the organic components such as resin is then calculated from the difference. Next, the obtained mass is divided by the specific gravity of each to calculate the volume of the (SD) thermally conductive filler and organic components such as resin.

[0178] <Contents of specific elements and contents of specific ions in the film> From the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability, the film of the present invention preferably satisfies at least one of the following conditions (S1a), (S2a), (S3a), (S1b), (S2b), and (S3b). 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 even more preferably satisfies at least one of the following conditions (S1a), (S2a), and (S3a) and at least one of the following conditions (S1b), (S2b), and (S3b). When the following (S1a) is satisfied, it is preferable to satisfy the following (S1b). When the following (S2a) is satisfied, it is preferable to satisfy the following (S2b). When the following (S3a) is satisfied, it is preferable to satisfy the following (S3b). When the film of the present invention satisfies the following condition (S1b), it is preferable that the film contains ions containing boron element and satisfies the following condition (S1a). When the film of the present invention satisfies the following condition (S2b), it is preferable that the film contains ions containing phosphorus element and satisfies the following condition (S2a). When the film of the present invention satisfies the following condition (S3b), it is preferable that the film contains chloride ions and bromide ions and satisfies the following condition (S3a). (S1a) The content of boron element in the film is 5.0 mass% or less. (S2a) The content of phosphorus element in the film is 1,000 mass ppm or less. (S3a) The total content of chlorine element and bromine element in the film is 1,000 mass ppm or less. (S1b) 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 5,000 mass ppm or less. (S3b) The total content of chloride ions and bromide ions in the film is 1,000 mass ppm or less.

[0179] When configured as described above, the film of the present invention preferably contains the following (I) and / or (II): (I) one or more components selected from the group consisting of a component containing boron element, a component containing phosphorus element, a component containing chlorine element, and a component containing bromine element; (II) one or more components selected from the group consisting of a component containing a boron-based cation, a component containing the following boron-based anion, a component containing a phosphorus-based cation, a component containing the following phosphorus-based anion, and a component containing the following halogen anion; Boron-based anion: one or more components selected from the group consisting of borate ion, boronate ion, borinate ion, tetraphenylborate ion, tetrafluoroborate ion, and trifluoroborate ion; Phosphorus-based anion: one or more components selected from the group consisting of phosphate ion, phosphite ion, hypophosphite ion, and hexafluorophosphate ion; Halogen anion: chloride ion and / or bromide ion.

[0180] 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, still more preferably 0.070% by mass or more, and particularly preferably 0.10% by mass or more, while 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, and particularly preferably 1.0% by mass or less.

[0181] The content of 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, still more preferably 0.070 mass ppm or more, and particularly preferably 0.10 mass ppm or more. On the other hand, the content of 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, still more preferably 50 mass ppm or less, still more preferably 30 mass ppm or less, even more preferably 10 mass ppm or less, still 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.

[0182] The preferred range of the total content of chlorine and bromine elements in the film is the same as the above-mentioned upper and lower limits of the content of phosphorus element.

[0183] The total content of ions containing 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, still more preferably 0.070% by mass or more, and particularly preferably 0.10% by mass or more, while 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 particularly preferably 1.0% by mass or less.

[0184] The total content of ions containing phosphorus in the film is preferably 0.010 ppm by mass or more, more preferably 0.030 ppm by mass or more, even more preferably 0.050 ppm by mass or more, still more preferably 0.070 ppm by mass or more, and particularly preferably 0.10 ppm by mass or more. On the other hand, the total content of ions containing phosphorus in the film is preferably 3,000 ppm by mass or less, more preferably 1,000 ppm by mass or less, even more preferably 500 ppm by mass or less, still more preferably 300 ppm by mass or less, still more preferably 100 ppm by mass or less, still more preferably 50 ppm by mass or less, still more preferably 30 ppm by mass or less, particularly preferably 10 ppm by mass or less, and particularly preferably 5.0 ppm by mass or less.

[0185] 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, still more preferably 0.070 mass ppm or more, and particularly preferably 0.100 mass ppm or more, while 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, still more preferably 50 mass ppm or less, still more preferably 30 mass ppm or less, still more preferably 10 mass ppm or less, still 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.

[0186] With the above-described configuration, it is believed that the boron, phosphorus, chlorine, or bromine element interacts with the surface of the component to be bonded. Boron has an empty 3p orbital, and it is believed that electron acceptance utilizing this empty orbital facilitates the formation of a coordinate bond with the surface of the component. Furthermore, phosphorus has an unshared electron pair, and it is believed that efficient electron donation utilizing the empty 3d orbital facilitates the formation of a coordinate bond with the surface of the component. Furthermore, chlorine and bromine have many unshared electron pairs, and it is believed that electron donation utilizing these electron pairs facilitates the formation of a coordinate bond with the surface of the component. These actions allow the material to function as an anchor at the interface with the component at extremely low temperatures, thereby improving conformability to each component, and improving adhesion and thermal cycle reliability.

[0187] <Content of elemental fluorine and content of fluoride ions in film> From the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability, the film of the present invention preferably satisfies at least one of the following conditions (S3α) and (S3β). From the same viewpoint, the film of the present invention more preferably satisfies the following condition (S3α), and even more preferably satisfies the following condition (S3α) and also the following condition (S3β). When the film of the present invention satisfies the following condition (S3β), the fluoride ions in the film satisfy the following condition (S3α): (S3α) The content of elemental fluorine in the film is 1,000 ppm by mass or less (S3β) The content of fluoride ions in the film is 1,000 ppm by mass or less.

[0188] When configured as described above, the film of the present invention preferably contains the following (III) and / or (IV): (III) a component containing elemental fluorine; and (IV) a component containing fluoride ions.

[0189] The content of elemental fluorine in the film is preferably more than 0.000 ppm by mass, more preferably 0.010 ppm by mass or more, even more preferably 0.030 ppm by mass or more, even more preferably 0.050 ppm by mass or more, particularly preferably 0.070 ppm by mass or more, and particularly preferably 0.10 ppm by mass or more. On the other hand, the content of elemental fluorine in the film is preferably 500 ppm by mass or less, more preferably 300 ppm by mass or less, even more preferably 100 ppm by mass or less, even more preferably 50 ppm by mass or less, even more preferably 30 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5.0 ppm by mass or less, particularly preferably 3.0 ppm by mass or less, and particularly preferably 1.0 ppm by mass or less.

[0190] 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, still more preferably 0.050 mass ppm or more, particularly preferably 0.070 mass ppm or more, and particularly preferably 0.10 mass ppm or more. On the other hand, 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, still more preferably 50 mass ppm or less, still more preferably 30 mass ppm or less, even more preferably 10 mass ppm or less, still 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.

[0191] Elemental fluorine has many unshared electron pairs, and it is thought that by including elemental fluorine in the film, coordination bonds to the surface of the member are easily formed due to electron donation utilizing these electron pairs.

[0192] 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. When the content of elemental fluorine and / or the content of fluoride ions in the film exceeds 0.000 ppm by mass, the film of the present invention preferably contains the binder resin (SA) or the thermally conductive filler (SD) having a fluorine atom or a fluoride ion in its structure, or further containing a component containing elemental fluorine and / or a component containing fluoride ions.

[0193] When the film of the present invention contains a (SB) compound or a (SC) compound and the content of elemental fluorine and / or fluoride ions in the film exceeds 0.000 mass ppm, the film of the present invention preferably contains the (SA) binder resin, the (SD) thermally conductive filler, the (SB) compound, or the (SC) compound having a fluorine atom or a fluoride ion in its structure, or further contains a component containing a fluorine element and / or a component containing a fluoride ion.

[0194] By limiting the content of compounds containing fluorine atoms in their structures or components containing fluorine atoms in the film to a specific value or less, the content of fluorine atoms, fluoride ions, or anions containing fluorine atoms derived from these components in these components is also limited to a specific value. This is thought to improve local interactions with the surfaces of the components to be joined due to the hydrogen bonds of each component in the film and the electronegativity of fluorine atoms. Furthermore, intentionally limiting the content of these components to a specific value or less is thought to control the polarization structure and charge balance in the film, thereby suppressing the effects of ionic components that adversely affect the mechanical properties of the film during thermal cycling. These effects are thought to allow the film to function as an anchor at the interface with the components at extremely low temperatures, improving conformability to each component, adhesion, and thermal cycling reliability.

[0195] <Content of Platinum Element and Content of Ions Containing Platinum Element in Film> From the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability, the film of the present invention preferably satisfies at least one of the following conditions (S4a) and (S4b). 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 the following condition (S4b). When the film of the present invention satisfies the following condition (S4b), the following condition (S4a) is satisfied by the ions containing platinum element in the film. (S4a) The content of platinum element in the film is 1,000 ppm by mass or less. (S4b) The total content of ions containing platinum element in the film is 5,000 ppm by mass or less.

[0196] In the above-described configuration, the film of the present invention preferably contains a component containing platinum element and / or a component containing platinum cation. The component containing platinum element is preferably platinum alone or an organic platinum compound. The component containing platinum cation is preferably a platinum halide, platinum hydroxide, platinum alkoxide compound, platinum chelate compound, or platinum carboxylate.

[0197] The platinum content in the film is preferably 0.010 ppm by mass or more, more preferably 0.030 ppm by mass or more, even more preferably 0.050 ppm by mass or more, still more preferably 0.070 ppm by mass or more, and particularly preferably 0.10 ppm by mass or more, while the platinum content in the film is preferably 500 ppm by mass or less, more preferably 300 ppm by mass or less, even more preferably 100 ppm by mass or less, still more preferably 50 ppm by mass or less, particularly preferably 30 ppm by mass or less, and particularly preferably 10 ppm by mass or less.

[0198] The total content of ions containing 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, still more preferably 0.070 mass ppm or more, and particularly preferably 0.10 mass ppm or more, while the total content of ions containing platinum element 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, still more preferably 300 mass ppm or less, particularly preferably 100 mass ppm or less, and particularly preferably 50 mass ppm or less.

[0199] With the above-mentioned structure, it is believed that the platinum element is coordinated to the surface of the components to be joined and functions as an anchor at the interface with the components at extremely low temperatures, which is presumed to improve the conformability to each component, adhesion, and thermal cycle reliability.

[0200] <Content of specific silicon compounds and content of cyclic silicone compounds in the film> From the viewpoint of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability, the film of the present invention preferably satisfies at least one of the following conditions (S5a) and (S5b). 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 the following condition (S5b). (S5a) The total content of organosilane compounds having 1 to 2 silicon atoms (hereinafter referred to as "specific silicon compounds") in the film is 1,000 ppm by mass or less. (S5b) The total content of cyclic silicone compounds in the film is 1,000 ppm by mass or less.

[0201] The specific silicon compound preferably has a methyl group, a phenyl group, a hydroxy group, an epoxy group, an amino group, a styryl group, a (meth)acryloyl group, a vinyl group, or an allyl group.

[0202] The number of silicon atoms contained in the cyclic silicone compound is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more, and particularly preferably 10 or more. On the other hand, the number of silicon atoms contained in the cyclic silicone compound is preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less.

[0203] The specific silicon compound and cyclic silicone compound preferably have an alkoxy group and / or a silanol group.The total number of the alkoxy group and the silanol group is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.On the other hand, the total number of the alkoxy group and the silanol group is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0204] The total content of the 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, even more preferably 0.070 mass ppm or more, and particularly preferably 0.10 mass ppm or more.On the other hand, the total content of the specific silicon compounds 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, particularly preferably 30 mass ppm or less, and particularly preferably 10 mass ppm or less.

[0205] The total content of the 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, even more preferably 0.070 mass ppm or more, and particularly preferably 0.10 mass ppm or more. On the other hand, the total content of the cyclic silicone compounds 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, particularly preferably 30 mass ppm or less, and particularly preferably 10 mass ppm or less.

[0206] It is believed that the specific silicon compound reacts with hydroxyl groups and / or silanol groups on the surface of the component, thereby functioning as an anchor at the interface with the component at extremely low temperatures, improving conformability to each component, adhesion, and thermal cycle reliability.

[0207] <Crosslinking agent or compound having a structure derived from a crosslinking agent> 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 "crosslinking agent or similar compound"). The crosslinking agent or similar compound may be a crosslinking agent or a compound having a structure derived from a crosslinking agent. The crosslinking agent may be a compound in a composition for forming the film of the present invention. The crosslinking agent refers to a compound having a crosslinkable group, a radical polymerizable group, a cationically polymerizable group, or an anionically polymerizable group that can react with a resin or the like.

[0208] As described above, the crosslinking agent or other compound is preferably a compound that forms or has formed a crosslinked structure with the binder resin (SA). 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 compound (SB), and may also be a compound having an epoxy group different from the above-mentioned compound (SB).

[0209] The crosslinking agent and other compounds described above are suitable for improving the mechanical properties of the film due to the crosslinked structure formed with the binder resin (SA). It is also believed that the structure derived from the crosslinking agent improves adhesion and other properties due to interactions with various components.

[0210] <Curing accelerator or compound having a structure derived from a curing accelerator> 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 "compound such as a curing accelerator"). The compound such as a curing accelerator may be a curing accelerator or a compound having a structure derived from a curing accelerator. The curing accelerator may be a compound in a 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 (SB) compound or crosslinking agent.

[0211] The curing accelerator or other compound is preferably a compound that forms or has formed a crosslinked structure with the above (SB) compound or crosslinking agent. The crosslinked structure is preferably formed by a reaction, and may be formed by heating, irradiation with energy rays, or the like, but is not particularly limited thereto. 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 may be a compound different from the above (SC) compound, or may be a compound having an amino group different from the above (SC) compound. The curing accelerator is also preferably a latent curing accelerator that liberates the above substituents or structures upon reaction, heating, or irradiation with energy rays.

[0212] The curing accelerator compounds described above are suitable for improving the mechanical properties of the film due to the crosslinked structure formed with the (SB) compound or the crosslinking agent. It is also believed that the interaction between the curing accelerator and each component improves adhesion.

[0213] From the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability, the curing accelerator is preferably a compound having a silicone structure and / or a siloxane structure, at least two alkylene groups bonded to silicon atoms in the silicone structure or siloxane structure, and further having an acid anhydride group (hereinafter referred to as a “specific acid anhydride compound”).

[0214] The silicone structure and siloxane structure of the specific acid anhydride compound are preferably bonded to at least two alkylene groups, and are preferably divalent or higher structures via these alkylene groups.The number of silicon atoms of the specific acid anhydride compound 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 of 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 monoalkyl siloxane structure.

[0215] The specific acid anhydride compounds as described above are suitable for adjusting the shear strain at −50° C. to within a range of 0.70 to 20 and / or adjusting the elastic modulus at −50° C. to within a range of 0.10 to 200 MPa due to the flexible skeleton derived from the silicone structure or siloxane structure.

[0216] <Other Compounds or Compounds Having a Structure Derived from Other Compounds> The film of the present invention may contain other compounds or compounds having a structure derived from other compounds. These compounds may be other compounds or compounds having a structure derived from other compounds. The other compounds may be compounds in the composition for forming the film of the present invention. The other compounds are preferably metal alkoxide compounds, metal chelate compounds, or surfactants.

[0217] 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-mentioned metal alkoxide compound and the metal chelate compound are suitable for improving the mechanical properties of the film due to the crosslinked structure formed with the (SA) binder resin, the (SB) compound, or the crosslinking agent. Furthermore, it is presumed that these compounds function as anchors at the interface with the member, thereby improving adhesion, etc.

[0218] The surfactant is preferably a fluororesin-based surfactant, a silicone-based surfactant, or an acrylic resin-based surfactant. Such surfactants are suitable for bonding another member to the surface of the film by suppressing protrusions on the surface of the film. It is presumed that suppressing protrusions on the surface in this way increases the contact area with the other member and promotes interaction, thereby improving adhesion, etc.

[0219] <Solvent> When the film of the present invention is in a semi-cured state (B-stage) described below, a portion of the solvent may remain. The solvent may be a portion of the solvent in the composition for forming the film of the present invention. 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.

[0220] <Method for Producing Film of the Present Invention> A method for producing a composition for forming a film of the present invention will be exemplified below. One method is to add a resin, various additives, a filler component, and a solvent, mix them using a stirrer or kneader, and then mix them using a bead mill or a three-roll mill.

[0221] A method for producing the film of the present invention will be exemplified below. One example is a method in which a coating film of the composition is formed on a support described below by a method such as coating or printing, and then the coating film is dried under reduced pressure to remove the solvent as needed, and then the coating film is heated at 40 to 150° C. Thereafter, a protective film described below may be laminated on the formed film as needed.

[0222] <Physical Properties of Film> In a first embodiment of the film of the present invention, the modulus of elasticity at -50°C is preferably 0.10 to 200 MPa. In a second embodiment of the film of the present invention, the modulus of elasticity at -50°C is preferably 0.10 to 200 MPa. In the film of the present invention, the modulus of elasticity 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 viewpoints of improving adhesion at extremely low temperatures of about -50°C and improving reliability in thermal cycling. On the other hand, the modulus of elasticity 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 viewpoints of improving adhesion at extremely low temperatures of about -50°C and improving reliability in thermal cycling. 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.

[0223] With the above-described configuration, the low elastic modulus at extremely low temperatures of about -50°C reduces internal stress caused by the difference in thermal expansion coefficient between the components to which the film is joined, improving conformity to each component, which is presumably improving adhesion and thermal cycle reliability.

[0224] The film of the present invention has a thermal conductivity at 25°C of 0.10 to 5.0 W / (m·K). From the viewpoints of improving adhesion and improving thermal cycle reliability, the thermal conductivity at 25°C of the film of the present invention is preferably 0.30 W / (m·K) or more, more preferably 0.50 W / (m·K) or more, even more preferably 0.70 W / (m·K) or more, and particularly preferably 1.0 W / (m·K) or more. On the other hand, from the viewpoint of improving thermal cycle reliability, the thermal conductivity at 25°C is preferably 4.0 W / (m·K) or less, more preferably 3.0 W / (m·K) or less, even more preferably 2.5 W / (m·K) or less, and particularly preferably 2.0 W / (m·K) or less.

[0225] In a first embodiment of the film of the present invention, the shear strain at -50°C is 0.70 to 20. In a second embodiment of the film of the present invention, the shear strain at -50°C is preferably 0.70 to 20. In the film of the present invention, the shear strain at -50°C is preferably 1.0 or more, more preferably 1.5 or more, even more preferably 2.0 or more, and particularly preferably 2.5 or more, from the viewpoints of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability. On the other hand, the shear strain at -50°C is preferably 17 or less, more preferably 15 or less, even more preferably 12 or less, and particularly preferably 10 or less, from the viewpoints of improving adhesion at extremely low temperatures of about -50°C and improving thermal cycle reliability.

[0226] By adopting the above-described configuration, the material has flexibility that can mitigate the difference in thermal expansion coefficient between components even at extremely low temperatures, and it is thought that this improves the material's ability to conform to each component, thereby improving adhesion and thermal cycle reliability.

[0227] From the viewpoint of improving adhesion, the thickness of the film of the present invention is preferably 5.0 μm or more, more preferably 20 μm or more, even more preferably 50 μm or more, still more preferably 100 μm or more, and particularly preferably 150 μm or more. On the other hand, from the viewpoint of improving thermal cycle reliability, the thickness of the film of the present invention is preferably 500 μm or less, more preferably 400 μm or less, even more preferably 350 μm or less, and particularly preferably 300 μm or less.

[0228] <Laminate> The laminate of the present invention will be described below. When referring to the laminate of the present invention, this 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 referring to a laminate of a specific embodiment, it will be referred to as the first embodiment of the laminate of the present invention, etc. However, the present invention is not limited to the following embodiments, and various modifications are naturally possible within the scope that can achieve the object of the invention and does not deviate from the gist of the invention.

[0229] <Semi-cured film and laminate> From the viewpoint of improving adhesion, the elastic modulus of the film of the present invention 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, and particularly preferably 0.30 MPa or more. On the other hand, 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.

[0230] 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 a crosslinked structure is not formed or a crosslinked structure is formed by a partial reaction, but the film has fluidity, or a state in which the film is in this state. For example, the semi-cured state refers to a state in which the coating film is applied to a substrate or the like, and then dried under reduced pressure to remove the solvent, or a state in which the coating film is heated to 40 to 150°C and dried, and is soluble in an organic solvent or an alkaline solution.

[0231] A first aspect of the laminate of the present invention is a laminate having a support and a film of the present invention, in which the film of the present invention is disposed on the support. In the first aspect of the laminate of the present invention, the modulus of elasticity of the film at 25°C is preferably 0.010 to 1.0 MPa, and the film is preferably in a semi-cured state.

[0232] The above-described structure is preferable from the viewpoint of improving adhesion and ease of handling, and is suitable for disposing the film on a base member or ceramic dielectric member, which will be described later.

[0233] <Support> A first embodiment of the laminate of the present invention has a support. The support is preferably a flexible substrate from the viewpoints of improving adhesion to the film, flexibility, and ease of 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 also be a rigid substrate. Examples of rigid substrates include a glass substrate, a quartz substrate, a crystal substrate, and a sapphire substrate. The surface of the support facing the film may be surface-treated with a silane coupling agent or the like from the viewpoints of improving adhesion to the film and improving peelability. The thickness of the support is preferably 10 to 200 μm from the viewpoint of ease of handling.

[0234] In a first aspect of the laminate of the present invention, from the viewpoint of improving handleability and protecting the surface of the film, it is preferable that the laminate has a first support, the film of the present invention, and a second support in this order. It is also preferable that the first support and the second support have different thicknesses.

[0235] Examples and preferred descriptions of the first support and the second support are the same as those of the supports described above. The second support is preferably a protective film, and is 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 handleability, the second support preferably has low adhesive strength to the film.

[0236] <First Embodiment of Laminate> Fig. 1 shows a schematic cross-sectional view of one example of the configuration of a laminate according to a first embodiment of the present invention. The 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 preferably the film of the present invention and is 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.

[0237] <Film and Laminate as Cured Product of Composition> 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 by a reaction and the loss of fluidity of the film, or the state in which this occurs. The reaction is not particularly limited, and may be caused by heating, irradiation with energy rays, or the like, but is preferably caused by heating. The state in which a crosslinked structure is formed by heating and the film loses its fluidity is called thermal curing.

[0238] Heating conditions include, for example, heating at 150 to 500°C for 5 to 300 minutes. Heating methods include, for example, heating using an oven, a hot plate, infrared radiation, a flash annealing device, or a laser annealing device. Treatment atmospheres include, for example, air, oxygen, nitrogen, helium, neon, argon, krypton, or xenon atmospheres, gas atmospheres containing 1.0 ppm by mass or more but less than 10,000 ppm by mass (0.00010% by mass or more but less than 1.0% by mass) of oxygen, gas atmospheres containing 10,000 ppm by mass (1.0% by mass) or more of oxygen, and vacuum.

[0239] The film of the present invention can exhibit both high adhesion for bonding members together even at extremely low temperatures of around −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 to form a laminate in which the substrate processing step is performed at a temperature of 0°C or lower. The temperature in 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. Meanwhile, the temperature in the 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.

[0240] The film of the present invention may be used in a substrate processing step at a temperature exceeding 0° C., or may be used to form a laminate in which the substrate processing step is carried out at a temperature exceeding 0° C. In this case, the temperature in 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. On the other hand, 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.

[0241] The film preferably has a plurality of through holes. The through holes are preferably formed by a punch hole method, a press processing 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.

[0242] A second aspect of the laminate of the present invention is a laminate having a base member, the film of the present invention, and a ceramic dielectric member in this order, wherein the base member and the ceramic dielectric member have different thermal expansion coefficients. In the second aspect of the laminate of the present invention, it is preferable that the film is a cured product of a composition. In the second aspect of the laminate of the present invention, it is also preferable that 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.

[0243] The above-described configuration is preferable from the viewpoint of improving adhesion when joining a base member and a ceramic member, and the effect of suppressing peeling of the members is remarkable even when the thermal expansion coefficients of the base member and the ceramic dielectric member are different.

[0244] From the viewpoint of improving adhesion and heat dissipation efficiency in the substrate processing step, 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 even more preferably 10 ppm / K or more. On the other hand, the 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.

[0245] <Contents of specific elements and contents of specific ions in the film of the laminate> From the viewpoint of improving adhesion at extremely low temperatures of about −50° C. and improving thermal cycle reliability, the film of the laminate of the present invention preferably satisfies at least one of the above conditions (S1a), (S2a), (S3a), (S1b), (S2b), and (S3b) similarly to the film of the present invention. When configured as described above, the film of the laminate of the present invention preferably contains the above conditions (I) and / or (II) similarly to the film of the present invention.

[0246] The preferred ranges of the content of boron element, the preferred range of the content of phosphorus element, and the preferred range of the total content of chlorine element and bromine element in the film of the laminate are also the same as those of the film of the present invention. The preferred ranges of the total content of ions containing boron element, the preferred range of the total content of ions containing phosphorus element, and the preferred range of the total content of chloride ions and bromide ions in the film of the laminate are also the same as those described above.

[0247] The film of the laminate of the present invention preferably satisfies at least one of 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. When configured as described above, the film of the laminate of the present invention preferably contains a component containing platinum element and / or a component containing platinum cations similarly to the film of the present invention.

[0248] The preferred range of the platinum content in the film of the laminate is the same as that of the film of the present invention. The preferred range of the total content of ions including platinum in the film of the laminate is the same as that of the film of the present invention.

[0249] <Content of specific silicon compound and content of cyclic silicone compound in film of laminate> From the viewpoint of improving adhesion at cryogenic temperatures of about −50° C. and improving thermal cycle reliability, the film of the laminate of the present invention preferably satisfies at least one of the above conditions (S5a) and (S5b) in the same manner as the film of the present invention. When configured as described above, the examples and preferred descriptions regarding the specific silicon compound and cyclic silicone compound are also as described above.

[0250] The preferred ranges for the total content of the specific silicon compounds and the preferred ranges for the total content of the cyclic silicone compounds in the film of the laminate are also the same as those described above.

[0251] <Base Member> A second aspect of the laminate of the present invention has a base member. The base member is preferably formed of a metal or various composite materials. The metal is preferably aluminum, titanium, or an alloy thereof. The composite material is preferably formed by melting and pressurizing a porous ceramic containing silicon carbide as a primary component with an aluminum alloy containing aluminum as a primary component. The aluminum alloy in the composite material may contain silicon or magnesium, or may contain other elements.

[0252] <Ceramic dielectric member> A second embodiment of the laminate of the present invention has a ceramic dielectric member. The ceramic dielectric member is preferably a flat substrate made of sintered ceramic. From the viewpoints of mechanical strength, abrasion resistance, plasma resistance, thermal conductivity, and insulating properties, the ceramic dielectric member is preferably made of aluminum oxide (alumina: Al ２ O ３ ), aluminum nitride, silicon carbide, silicon nitride, and yttrium oxide (yttria: Y ２ O ３ It is preferable that the composition contains one or more selected from the group consisting of aluminum oxide and aluminum nitride, and more preferable that the composition contains aluminum oxide or aluminum nitride as a main component. The main component refers to the component that is contained in the largest amount by mass among the constituent components.

[0253] <Second embodiment of laminate> Fig. 2 shows a schematic cross-sectional view of one example of the configuration of a second embodiment of the laminate. The laminate 200A shown in Fig. 2 is a laminate having 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.

[0254] <Electrostatic Chuck Comprising Laminate> The electrostatic chuck of the present invention comprises a laminate including the film of the present invention. The film of the present invention can combine high adhesion for bonding members together even at extremely low temperatures of about −50°C with high thermal cycle reliability. Therefore, the film of the present invention is preferably used in substrate processing steps at temperatures of 0°C or lower, and more preferably used to form an electrostatic chuck in a substrate processing step at temperatures of 0°C or lower. That is, the film of the present invention is suitable for use as an electrostatic chuck. The film of the present invention is particularly suitable for use as an electrostatic chuck used at temperatures of 0°C or lower, and even more particularly suitable for use as an electrostatic chuck used at temperatures of −50°C or lower. The preferred temperature ranges for substrate processing steps using an electrostatic chuck are the same as those for substrate processing steps using the above-mentioned laminate. 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.

[0255] The film of the present invention may be used in a substrate processing step at a temperature exceeding 0° C., or may be used to form an electrostatic chuck in a substrate processing step at a temperature exceeding 0° C. In this case, the preferred temperature range for the substrate processing step using the electrostatic chuck is also the same as the preferred temperature range for the substrate processing step using the above-mentioned laminate.

[0256] <Article Comprising Laminate> The laminate of the present invention can be applied to various articles. Such articles are preferably those comprising an electrostatic chuck comprising the laminate of the present invention. Examples of articles comprising such a laminate or an electrostatic chuck include electronic devices, mobile objects, buildings, and windows. Examples of electronic devices include display devices, semiconductor devices, metal-clad laminates, industrial devices, medical devices, and construction devices. Examples of mobile objects include vehicles, trains, airplanes, and heavy machinery. Examples of buildings include residences, stores, offices, buildings, and factories. Examples of windows include windows for electronic devices, windows for mobile objects, and windows for buildings.

[0257] <Plasma Processing Apparatus Comprising a Laminate> The plasma processing apparatus of the present invention comprises a plasma generation source and the laminate of the present invention. The plasma processing apparatus of the present invention preferably comprises a plasma generation source and an electrostatic chuck comprising the laminate of the present invention. This configuration is advantageous from the viewpoints of improving the aspect ratio and reducing the process time in the etching step, and is preferably used for increasing the density and integration of 3D-NAND memories and the like.

[0258] The plasma processing apparatus of the present invention is an apparatus in which a substrate to be processed, such as a semiconductor wafer, is placed on a laminate (preferably an electrostatic chuck) provided in a vacuum chamber, and a high-frequency voltage is applied in a vacuum environment to generate plasma to perform etching, etc. The electrostatic chuck in the plasma processing apparatus is a laminate formed by bonding, with a film, a ceramic dielectric member incorporating a heater electrode and an electrostatic electrode and a base member serving as a cooling plate having a refrigerant flow path formed therein.

[0259] A plasma processing apparatus is provided with a mounting table for placing a semiconductor wafer inside a vacuum chamber. The mounting table is primarily composed of an electrostatic chuck and a cooler that controls the temperature of the electrostatic chuck. In recent years, high processing accuracy has been required in the manufacture of semiconductor devices, and the formation of high-aspect-ratio vias requires etching at extremely low temperatures of -30°C or below. Therefore, it is necessary to cool the ceramic dielectric member by cooling the base member, which serves as a cooling plate, to -30°C or below. The film of the present invention that bonds these members together can reduce the thermal resistance at the interface between the two members, thereby improving cooling efficiency.

[0260] <Article Comprising Film and Article Comprising Laminate> The article comprising the film of the present invention and the laminate having the film of the present invention are also suitable for use in applications other than electrostatic chucks. In addition to the articles exemplified above, other applications include, for example, vacuum chucks.

[0261] <Method for Producing Laminate> The method for producing a laminate of the present invention comprises the steps of arranging a base member, arranging the film of the present invention, and arranging a ceramic dielectric member.

[0262] The step of disposing the film of the present invention is preferably performed after the step of disposing the base member, and is preferably disposed on the base member. That is, the method for producing the laminate of the present invention preferably includes a step of disposing the film of the present invention after the step of disposing the base member, and further includes a step of disposing a ceramic dielectric member after the step of disposing the film of the present invention.

[0263] The step of disposing the film of the present invention is preferably performed after the step of disposing the ceramic dielectric member, or is preferably performed on the ceramic dielectric member. That is, the method for producing the laminate of the present invention preferably includes a step of disposing the film of the present invention after the step of disposing the ceramic dielectric member, and also preferably includes a step of disposing a base member after the step of disposing the film of the present invention.

[0264] <Step of placing a base member> The step of placing a base member is preferably a step of placing a base member on an article, and also preferably a step of placing a base member fixed to an article. If the step of placing a base member occurs after the step of placing the film of the present invention, it is preferably placed on the film of the present invention. Furthermore, the step of placing a base member is also preferably a step of forming a base member on a support, placing the base member having the support, and then peeling the support from the base member. It is preferable that the base member having the support is placed by bonding it with an adhesive or the like.

[0265] Examples of the article include electronic devices, mobile objects, buildings, and windows. Examples of the electronic devices include display devices, semiconductor devices, metal-clad laminates, industrial devices, medical devices, and construction devices. Examples of the mobile objects include vehicles, trains, airplanes, and heavy machinery. Examples of the buildings include residences, stores, offices, buildings, and factories. Examples of the windows include windows for electronic devices, mobile object windows, and building windows.

[0266] The base member may be a commercially available metal member. The step of disposing the base member may be a step of disposing a commercially available metal member as the base member on the article.

[0267] <Step of placing a ceramic dielectric member> The step of placing a ceramic dielectric member is preferably a step of placing the ceramic dielectric member on an article. If the step of placing a ceramic dielectric member is performed after the step of placing the film of the present invention, it is preferable to place it on the film of the present invention. The step of placing a ceramic dielectric member is also preferably a step of forming a ceramic dielectric member on a support, placing the ceramic dielectric member having the support, and then peeling the support from the ceramic dielectric member. The ceramic dielectric member having the support is preferably placed by bonding it with an adhesive or the like. Examples of the article include the articles exemplified above as the base member.

[0268] The ceramic dielectric member may be a commercially available ceramic member. The step of disposing the ceramic dielectric member may be a step of disposing a commercially available ceramic member on the article as the ceramic dielectric member.

[0269] <Step of placing the film> The step of placing the film of the present invention is preferably a step of bonding the film of the present invention by thermocompression, and preferably bonding it onto a base member by thermocompression. Similarly, bonding it onto a ceramic dielectric member by thermocompression is also preferred. Furthermore, the step of placing the base member is also preferably bonding it onto the film of the present invention by thermocompression. Similarly, the step of placing the ceramic dielectric member is also preferably bonding it onto the film of the present invention by thermocompression. The method of bonding it by thermocompression is preferably a heat press treatment, a heat lamination treatment, or a heat vacuum lamination treatment.

[0270] When the film of the present invention having a first support and a second support is used, it is preferable to place the film of the present invention after peeling off the second support. The first support may be peeled off after the film of the present invention is placed, or may be peeled off during or after bonding the film of the present invention by a method such as thermocompression bonding.

[0271] The present invention will be described in more detail below with reference to examples, reference examples, and comparative examples, but the present invention is not limited to these. For compounds used in the following explanations or tables that use abbreviations, the names corresponding to the abbreviations are shown below. The structures of KF-8010, X-22-161A, X-22-161B, X-22-168A, and X-22-168AS are shown below. The term "major component" refers to the component that is contained in the largest amount by mass among the constituent components. ABPS: bis(3-amino-4-hydroxyphenyl)sulfone BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane BAPF: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene cyEpoTMS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane DMeDMS: dimethyldimethoxysilane DPhDMS: diphenyldimethoxysilane KF-8010: dimethyl silicone modified with amino groups at both ends represented by general formula (11a) (x = 7 to 11 is the main component), number average molecular weight: 860, amino group equivalent: 430 g / mol MePhDMS: methyldimethoxysilane MeTMS: methyltrimethoxysilane ODPA: 4,4'-oxydiphthalic dianhydride PET: polyethylene terephthalate PhTMS: phenyltrimethoxysilane TEGDM: triethylene glycol dimethyl ether X-22-161A: dimethyl silicone modified at both ends with amino groups represented by general formula (11a) (main component: x = 15 to 23), number average molecular weight: 1,600, amino group equivalent: 800 g / mol X-22-161B: dimethyl silicone modified at both ends with amino groups represented by general formula (11a) (main component: x = 32 to 44), number average molecular weight: 3,000, amino group equivalent: 1,500 g / mol X-22-168A: dimethyl silicone modified at both ends with carboxylic anhydride groups represented by general formula (12a) (main component: y = 18 to 26), number average molecular weight: 2,000, acid anhydride group equivalent: 1,000 g / mol X-22-168AS: Dimethyl silicone modified with carboxylic anhydride groups at both ends, represented by general formula (12a) (main component: y = 6 to 10), number average molecular weight: 1,000, acid anhydride group equivalent: 500 g / mol.

[0272]

[0273] <Synthesis Examples of Each Resin> The compositions of the resins obtained in Synthesis Examples 1 to 19 as the (SA) binder resin are shown in Tables 1 and 2.

[0274] Synthesis Example 1 Synthesis of Polyimide (PI-1) A 300 mL four-neck flask was equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a dropping funnel, and under a dry nitrogen stream, 40.00 g of X-22-168AS (0.040 mol; 100 mol% with respect to all carboxylic acid residues; molar ratio based on acid anhydride groups = 100) was weighed and dissolved with stirring at 60 ° C., and 79.33 g of TEGDM was dissolved. Then, while stirring at 60 ° C., 7.33 g of BAHF (0.020 mol; 50 mol% with respect to all amine residues; molar ratio based on amino groups = 50) was added and stirred for 1 hour. The mixture was then heated to 180°C and stirred for 3 hours, and then cooled to room temperature to obtain a polyimide (PI-1) solution with a solids concentration of 50% by mass. The resulting polyimide had a weight-average molecular weight of 29,000 and an imidization rate of 99%.

[0275] In Synthesis Examples 2 to 11, polyimides (PI-2) to (PI-11) were synthesized from each resin by the method described in Synthesis Example 1, while appropriately changing the monomer compounds to be used as monomers and the copolymerization ratios. The copolymerization ratios of the monomers are as shown in Table 1.

[0276] Synthesis Example 12 Synthesis of Silicone Resin (SR-1) 52.30 g (87 mol%) of DMeDMS, 2.73 g (3 mol%) of DPhDMS, 3.41 g (5 mol%) of MeTMS, 6.16 g (5 mol%) of cyEpoTMS, and 61.63 g of PGMEA were charged into a three-necked flask. Air was flowed into the flask at 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. After completion of the addition, the mixture was stirred at 40 ° C. for 30 minutes to hydrolyze the silane compound. After completion of hydrolysis, the bath temperature was raised to 70 ° C. and stirred for 1 hour, and then the bath temperature was raised to 115 ° C. Approximately 1 hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the solution was then heated and stirred for 2 hours (internal temperature: 100-110°C). The resin solution obtained after 2 hours of heating and stirring was cooled in an ice bath to obtain a silicone resin (SR-1) solution with a solids concentration of 40% by mass. The weight-average molecular weight of the resulting silicone resin was 4,000.

[0277] In Synthesis Examples 13 to 15, silicone resins (SR-2) to (SR-4) were synthesized by changing the monomer compounds and copolymerization ratios as appropriate for each resin using the method described in Synthesis Example 12. The copolymerization ratios of the monomers are shown in Table 2.

[0278] Synthesis Example 16 Synthesis of Polysiloxane (PS-1) 38.82 g (57 mol%) of MeTMS, 2.97 g (3 mol%) of PhTMS, 21.04 g (35 mol%) of DMeDMS, 6.16 g (5 mol%) of cyEpoTMS, and 57.15 g of PGMEA were charged into a three-neck flask. Air was flowed into the flask at 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. After completion of the addition, the mixture was stirred at 40 ° C. for 30 minutes to hydrolyze the silane compound. After completion of hydrolysis, the bath temperature was raised to 70 ° C. and stirred for 1 hour, and then the bath temperature was raised to 115 ° C. Approximately 1 hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature: 100-110°C). The resin solution obtained after 2 hours of heating and stirring was cooled in an ice bath to obtain a polysiloxane (PS-1) solution with a solids concentration of 40% by mass. The weight-average molecular weight of the resulting polysiloxane was 5,500.

[0279] In Synthesis Examples 17 to 19, polysiloxanes (PS-2) to (PS-4) were synthesized from each resin by the method described in Synthesis Example 16, while appropriately changing the monomer compounds to be used as monomers and the copolymerization ratios. The copolymerization ratios of the monomers are as shown in Table 2.

[0280]

[0281]

[0282] The structural units and structures of the resins obtained in each synthesis example and the resins used in each example, reference example, and comparative example are shown below.

[0283] Polyimides (PI-1) to (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). The fluorine element content in the resin structure of these polyimides is 29,300 ppm by mass for (PI-1), 15,600 ppm by mass for (PI-2), 4,700 ppm by mass for (PI-3), 3,100 ppm by mass for (PI-4), 3,300 ppm by mass for (PI-5), 5,400 ppm by mass for (PI-6), and 6,200 ppm by mass for (PI-7).

[0284] 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 acid 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.

[0285] Polyimide (PI-11) This polyimide has a main chain containing a polyimide structure. The fluorine content in the resin structure of this polyimide is 168,500 ppm by mass.

[0286] Silicone Resins (SR-1) to (SR-4) These silicone resins have a main chain containing a silicone resin structure, a difunctional organosilane unit and a trifunctional organosilane unit having an aliphatic group, a trifunctional organosilane unit having an aromatic group, and a trifunctional organosilane unit having an epoxy group.

[0287] Polysiloxanes (PS-1) to (PS-4) These polysiloxanes have a main chain containing a polysiloxane structure, a difunctional organosilane unit and a trifunctional organosilane unit having an aliphatic group, a trifunctional organosilane unit having an aromatic group, and a trifunctional organosilane unit having an epoxy group.

[0288] <Evaluation Methods in Examples, Reference Examples, and Comparative Examples> Evaluation methods in Examples, Reference Examples, and Comparative Examples are shown below.

[0289] (1) Weight-average molecular weight of resin For the polyimides (PI-1) to (PI-11), each resin was dissolved in N-methyl-2-pyrrolidone to prepare a 0.10% by mass N-methyl-2-pyrrolidone solution. The weight-average molecular weight was determined in terms of polystyrene using a GPC analyzer (Waters 2690; manufactured by Waters) under the following measurement conditions: <GPC measurement conditions> Detector: Waters 996 System controller: Waters 2690 Column oven: Waters HTR-B Thermocontroller: Waters TCM Column: TOSOH Guard Column Column: TOSOH TSK-GEL α-4000 Column: TOSOH TSK-GEL α-2500 Fluidized bed: N-methyl-2-pyrrolidone in which lithium chloride and phosphoric acid were dissolved at 0.050 mol / L each Development rate: 0.40 mL / min.

[0290] The weight average molecular weights of the silicone resins (SR-1) to (SR-4) and the polysiloxanes (PS-1) to (PS-4) were determined by measuring the polystyrene equivalent weight average molecular weight at around room temperature in accordance with JIS K7252-3 (2008) using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) and tetrahydrofuran or N-methyl-2-pyrrolidone as the fluidized bed.

[0291] (2) Imidization rate of polyimide The infrared absorption spectrum of each polyimide was measured using a Fourier transform infrared spectrophotometer (FT-720; manufactured by Horiba, Ltd.), and the absorption peak of the imide structure of the polyimide (1,780 cm －１ Nearby peaks and 1,377 cm －１ The presence or absence of a peak near 1,377 cm was confirmed. Each of the measured polyimides was heated at 350° C. for 1 hour to cause imide ring closure of the polyimide precursor structures (polyamic acid structures, polyamic acid ester structures, etc.) in each polyimide. After heating, the infrared absorption spectrum of each polyimide was measured to determine the difference between the peaks at 1,377 cm before and after heating. －１ The peak intensity of the polyimide after heating was taken as the imidization rate of 100%, and the imidization rate of the polyimide before heating was calculated.

[0292] (3) Average primary particle size of filler in filler dispersion Each filler was dispersed in methanol to prepare a methanol dispersion. The particle size distribution of each filler was measured by a laser diffraction / scattering method using a laser diffraction / scattering particle size distribution analyzer (LA-920; manufactured by Horiba, Ltd.). From the particle size distribution, D50, at which the cumulative particle size distribution from the small particle size side on a volume basis becomes 50%, was calculated. The measurement was performed twice, and the average value was taken as the average primary particle size of the filler in the filler dispersion.

[0293] (4) Average Primary Particle Diameter of Filler in Film A 250 μm thick film, which is a cured film of the composition, was prepared on a 38 μm thick PET film by the method described in Example 1 below. The PET film was peeled off, and the cross section of the film was photographed and analyzed using a transmission electron microscope to measure the primary particle diameter of the filler. The average value of 30 primary particles of the filler was determined as the average primary particle diameter of the filler in the film.

[0294] (5) Volume content 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 volume of each component was determined by dividing the obtained mass by its specific gravity. The volume of each component was calculated by setting the total volume of each component as 100% by volume.

[0295] (6) Contents of boron, phosphorus, chlorine, bromine, and fluorine in the film The contents of boron, phosphorus, chlorine, bromine, and fluorine were measured by combustion ion chromatography under the following measurement conditions. The film was burned and decomposed in the combustion tube of the analyzer, and the generated gas was absorbed in an absorption liquid, and then a portion of the absorption liquid was analyzed by ion chromatography. If the element content is not listed, it means that the element was not detected. <Combustion and absorption conditions> System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation) Electric furnace temperature: Inlet 900°C, Outlet 1000°C Gas: Ar / O ２ 200mL / min, O ２ 400 mL / min Absorption liquid: H ２O ２ 0.1 mass% Absorption solution volume: 5 mL <Conditions for ion chromatography and anion analysis> System: ICS1600 (manufactured by DIONEX) Mobile phase: 2.7 mmol / L Na ２ CO ３ , 0.3 mmol / L NaHCO ３ Flow rate: 1.50 mL / min Detector: electrical conductivity detector Injection volume: 100 μL.

[0296] (7) Platinum Content in Film The platinum content was measured by inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectrometry using a calibration curve based on a standard substance.

[0297] (8) Content of specific ions in the film The contents of ions containing boron, ions containing phosphorus, chloride ions, bromide ions, ions containing platinum, and fluoride ions were measured by ion chromatography under the following measurement conditions. The film was added to a 10 mmol / L aqueous potassium hydroxide solution and shaken for 2 hours to extract the ion components. The extract was filtered under the following conditions, and then analyzed for cationic and anionic components by ion chromatography. If the ion content is not listed, it means that the ion in question was not detected. <Filtration conditions> Membrane filter: 0.22 μmφ, 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> Apparatus: ICS-5000 ＋ (Manufactured by Thermo Fisher Scientific) Separation column: 2 mmφ×250 mm, IonPac AS11-HC-4 μm Eluent: potassium hydroxide / gradient Detector: electrical conductivity detector Sample injection volume: 100 μL.

[0298] (9) Thermal Conductivity of Film A 250 μm thick film, which is a cured film of the composition, was prepared on a 38 μm thick PET film by the method described in Example 1 below. The PET film was peeled off, and the thermal diffusivity of the film was measured using a laser flash thermal diffusivity measuring device (LFA447; manufactured by Netsch). The specific gravity of the film was measured by Archimedes' method, and the specific heat of the film was measured by differential scanning calorimetry. The thermal conductivity at 25°C was calculated from the obtained measured values ​​and the following formula: Thermal conductivity [W / (m·K)] = Thermal diffusivity [m ２ / s] x specific gravity [kg / m ３ ]×specific heat [J / (kg·K)].

[0299] (10) Elastic Modulus of Film A 250 μm thick film, which was a cured film of the composition, was prepared on a 38 μm thick PET film using the method described in Example 1 below. The PET film was peeled off, and the film was cut into a shape of 5.0 mm wide x 30 mm long. The elastic modulus of the film was measured using a dynamic viscoelasticity measuring device (DVA-200; manufactured by IT Measurement & Control Co., Ltd.). The measurement conditions were a temperature rise rate of 5.0°C / min and a measurement frequency of 1 Hz, and the storage elastic modulus was measured at each temperature from -100 to 300°C, and the elastic modulus at -50°C was determined.

[0300] (11) Film Shear Strain and Shear Adhesion Strength (Joint Adhesion) Using the method described in Example 1 below, a semi-cured film of the composition was prepared on a 38 μm thick PET film so that the thickness of the cured film was 250 μm. The laminate with the semi-cured film formed was cut into a shape of 12.5 mm wide x 25 mm long and thermally laminated on an aluminum plate of 25 mm wide x 100 mm long x 1.6 mm thick at 60 ° C and 0.10 MPa. Next, the PET film was peeled off, and an aluminum plate of 25 mm wide x 100 mm long x 1.6 mm thick was laminated and subjected to a heat press treatment at 180 ° C and 0.50 MPa for 1 hour to produce a laminate. Using a universal testing machine (AGX-V; manufactured by Shimadzu Corporation), a shear test was performed on the obtained laminate based on "JIS K6850". The test conditions were a temperature of -50°C and a pulling rate of 2.0 mm / min, and the stress at break and shear deformation 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. The results were judged as follows: A+, A, B+, B, C+, and C, which indicate a shear adhesive strength of 0.5 MPa or more, were rated as pass; A+, A, B+, and B, which indicate a shear adhesive strength of 1.5 MPa or more, were rated as good; and A+ and A, which indicate a shear adhesive strength of 1,000 MPa or more, were rated as excellent. A+: Shear adhesive strength is 3.0 or more. A: Shear adhesive strength is 2.5 or more and less than 3.0. B+: Shear adhesive strength is 2.0 or more and less than 2.5. B: Shear adhesive strength is 1.5 or more and less than 2.0. C+: 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 cannot be measured.

[0301] (12) Thermal Cycle Reliability of Film Using the method described in Example 1 below, a semi-cured film of the composition was prepared on a 38 μm thick PET film so that the thickness of the cured film was 250 μm. The laminate with the semi-cured film formed was cut into a shape of 150 mmφ and thermally laminated onto a 100 mmφ, 3.0 mm thick aluminum plate at 60°C and 0.10 MPa. Next, the PET film was peeled off, and a 100 mmφ, 3.0 mm thick alumina substrate was laminated and subjected to a heat press treatment at 120°C and 0.50 MPa for 24 hours to prepare a laminate. The presence or absence of delamination in the resulting laminate was observed using an ultrasonic flaw detector (FS300; manufactured by Hitachi Power Solutions Co., Ltd.). Furthermore, the presence or absence of cracks in the alumina substrate was visually inspected for appearance. Next, a thermal shock tester (TSE-11; manufactured by Espec Corporation) was used to conduct a thermal cycle test. The test conditions were a cycle consisting of 30 minutes of treatment at -65°C and 30 minutes of treatment at 100°C, and the presence or absence of delamination in the laminate was observed after 250 cycles, 500 cycles, and 1,000 cycles. The appearance was also visually inspected for cracks and the like in the alumina substrate. As an index of thermal cycle reliability, the number of cycles at which delamination, cracks, and the like occurred in the laminate and alumina substrate was measured. Note that if delamination, cracks, and the like occurred after the fabrication of the laminate, the above thermal cycle test was not performed, and the number of cycles was recorded as 0. If no delamination, cracks, and the like occurred after 1,000 cycles, the number of cycles was recorded as >1,000. Evaluation was performed as follows: A+, A, B, and C, which represent 250 or more cycles, were considered pass; A+, A, and B, which represent 500 or more cycles, were considered good; and A+ and A, which represent 1,000 or more cycles, were considered excellent. A+: No peeling, cracking, etc. occurred after 1,000 cycles. A: The number of cycles in which peeling, cracking, etc. occurred was 1,000. B: The number of cycles in which peeling, cracking, etc. occurred was 500. C: The number of cycles in which peeling, cracking, etc. occurred was 250. D: Peeling, cracking, etc. occurred after the laminate was produced, and the number of cycles was 0.

[0302] <Compounds used in each Example, Reference Example, and Comparative Example> A list and description of (SD) thermally conductive fillers (sd-1) to (sd-10) used in each Example, Reference Example, and Comparative Example are shown below.

[0303] [(SD) Thermally conductive filler] (sd-1): alumina particles (average primary particle diameter in filler dispersion: 3.0 μm, thermal conductivity: 20 W / (m·K), specific surface area: 1.62 m ２ / g) (sd-2): Alumina particles (average primary particle diameter in filler dispersion: 45 μm, thermal conductivity: 26 W / (m·K), specific surface area: 0.108 m ２ / g) (sd-3): Aluminum nitride particles (average primary particle diameter in filler dispersion: 30 μm, thermal conductivity: 170 W / (m·K), specific surface area: 0.196 m ２ / g) (sd-4): Alumina particles (average primary particle diameter in filler dispersion: 0.40 μm, thermal conductivity: 20 W / (m·K), specific surface area: 12.2 m ２ / g) (sd-5): Alumina particles (average primary particle diameter in filler dispersion: 10 μm, thermal conductivity: 26 W / (m K), specific surface area: 0.486 m ２ / g) (sd-6): Alumina particles (average primary particle diameter in filler dispersion: 60 μm, thermal conductivity: 26 W / (m·K), specific surface area: 0.081 m ２ / g) (sd-7): Aluminum nitride particles (average primary particle diameter in filler dispersion: 10 μm, thermal conductivity: 170 W / (m·K), specific surface area: 0.589 m ２ / g) (sd-8): Aluminum nitride particles (average primary particle diameter in filler dispersion: 50 μm, thermal conductivity: 170 W / (m·K), specific surface area: 0.118 m ２ / g) (sd-9): Alumina particles (average primary particle diameter in filler dispersion: 0.20 μm, thermal conductivity: 20 W / (m·K), specific surface area: 24.3 m ２ / g) (sd-10): Alumina particles (average primary particle diameter in filler dispersion: 0.80 μm, thermal conductivity: 20 W / (m·K), specific surface area: 6.08 m ２ / g).

[0304] In addition, compounds corresponding to (sb-1), which is the (SB) compound used in each of the Examples, Reference Examples, and Comparative Examples; (sc-1), (sc-2), (sc-3), and (sc-4), which are (SC) compounds; (ad-1), which is the curing accelerator; and (r-1), which is the amine compound used in the Comparative Examples, are also shown below.

[0305] [(SB) Compound] (sb-1) is a bifunctional epoxy compound having a structure containing an oxyalkylene group represented by general formula (21a), and is mainly composed of m=10.3. (sb-1) has a weight average molecular weight of 870 and an epoxy group equivalent of 435 g / mol.

[0306]

[0307] [(SC) Compounds] (sc-1): KF-8010 (sc-2): X-22-161A (sc-3): X-22-161B (sc-4): 1,3-bis(3-aminopropyl)tetramethyldisiloxane [Curing accelerator] (ad-1): 2-phenyl-4-methylimidazole [Amine compound] (r-1): 3,3'-diaminodiphenyl sulfone.

[0308] In addition, compounds containing boron, phosphorus, chlorine, bromine, platinum, or fluorine, and compounds containing boron-containing ions, phosphorus-containing ions, chloride ions, bromide ions, platinum-containing ions, or fluoride ions (hereinafter referred to as "specific element compounds") used in each of the Examples, Reference Examples, and Comparative Examples; the specific silicon compounds; and the cyclic silicone compounds 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 (Br-2): Tetraethylammonium bromide (Pt-1): Platinum elemental (Pt-2): Platinum(II) acetylacetonate (Si-1): Dimethyldimethoxysilane (Si-2): Diphenyldimethoxysilane (Si-3): Octamethylcyclotetrasiloxane (Si-4): Octaphenylcyclotetrasiloxane (F-1): Dodecyl fluoride (F-2): (butyltriethyl)ammonium fluoride.

[0309] <Preparation of Film-Forming Compositions> Compositions 1 to 67 used for film formation were prepared according to the formulations listed in Tables 3 to 10. In Tables 3 to 10, the numbers in parentheses indicate the parts by mass of the solid content of each component. After mixing the components, the mixture was kneaded five times using a three-roll mill to obtain viscous liquid compositions. Compositions 1 to 67 contained the TEGDM contained in each of the polyimide solutions described above as a solvent, while Compositions 22 to 29 contained the PGMEA contained in each of the silicone resin solutions or the polysiloxane solution described above as a solvent. The solid content concentration of Composition 1 was 87% by mass.

[0310] The amounts of the specific element compounds added were adjusted so that the contents of boron, phosphorus, chlorine, bromine, platinum, and fluorine in the compositions, as well as the contents of boron-containing ions, phosphorus-containing ions, chloride ions, bromide ions, platinum-containing ions, and fluoride ions, would be as shown in Tables 3 to 10. The amounts of the specific silicon compounds and cyclic silicone compounds added were adjusted so that the compositions would be as shown in Tables 3 to 10.

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319] Example 1 Preparation of Film Evaluation Sample Composition 1 was applied to a 38 μm thick PET film using a comma roll coater so that the thickness of the cured film was 250 μm, and then dried at 100° C. for 30 minutes to form a film, thereby preparing a semi-cured film of Composition 1. The prepared semi-cured film was heated at 180° C. for 4 hours to prepare a 250 μm thick film, which was a cured film of Composition 1.

[0320] Using this evaluation sample, the volume content of the filler in the film, and the thermal conductivity, elastic modulus, shear adhesive strength, shear strain, and thermal cycle reliability of the film were evaluated. The results are shown in Table 11.

[0321] Examples 2 to 64 and Comparative Examples 1 to 3 The same operations and evaluations as in Example 1 were carried out using each of the compositions shown in Tables 3 to 10. The evaluation results are summarized in Tables 11 to 18. For ease of comparison, the evaluation results of Example 3 are shown in Tables 12 to 15 and 17, and the evaluation results of Example 8 are shown in Table 16. The fluorine element contents in the compositions of Examples 1 to 7, Examples 11 to 21, Examples 30 to 64, and Comparative Examples 1 to 3 are as shown in Tables 3, 4, and 6 to 10, and the fluorine element contents in the films are as shown in Tables 11, 12, and 14 to 18.

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330] Comparative Example 1 contains (r-1) as an amine compound instead of (SC) compound, and because (r-1) has poor flexibility, the elastic modulus of the film at −50° C. is much higher than 200 MPa, and the shear strain at −50° C. is also lower than 0.70, resulting in poor thermal cycle reliability of the film.

[0331] 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.

[0332] Comparative Example 3 contains polyimide (PI-11) as the binder resin (SA). Because the flexibility of polyimide (PI-11) is poor, the elastic modulus of the film at -50°C is significantly high and the shear strain at -50°C is significantly small. Therefore, the thermal cycling reliability of the film is poor.

[0333] 10 First support 20 Second support 30 Film 40 Base member 50 Ceramic dielectric member 60 Film 100A, 200A Laminate

Claims

1. A film containing (SA) a binder resin and (SD) a thermally conductive filler, The (SD) thermal conductive filler comprises (SD1) a first thermal conductive filler and (SD2) a second thermal conductive filler. The average primary particle size of the (SD1) first thermally conductive filler is 1.0 to 200 μm, The average primary particle diameter of the (SD2) second thermally conductive filler is 0.010 μm or more and less than 1.0 μm, The shear strain at -50°C is 0.70 to 20, A film having a thermal conductivity of 0.10 to 5.0 W / (m·K) at 25°C.

2. The specific surface area of ​​the first thermally conductive filler (SD1) is 0.023 m² / g or more and 5.90 m² / g or less, The film according to claim 1, wherein the specific surface area of ​​the (SD2) second thermally conductive filler is 5.91 m² / g or more and 590 m² / g or less.

3. The film according to claim 1, wherein the (SD1) first thermal conductive filler and the (SD2) second thermal conductive filler include one or more selected from the group consisting of 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, titanium carbide particles, titanium nitride particles, titanium oxide particles, zirconium oxide particles, yttrium oxide particles, and iron oxide particles.

4. The film according to claim 1, wherein the content ratio of the (SD2) second thermal conductive filler is 20% by volume or more and 60% by volume or less, when the total of the (SD1) first thermal conductive filler and the (SD2) second thermal conductive filler is 100% by volume.

5. The film according to claim 1, wherein the modulus of elasticity at -50°C is 0.10 to 200 MPa.

6. A film containing (SA) a binder resin and (SD) a thermally conductive filler, The modulus of elasticity at -50°C is 0.10 to 200 MPa, The shear strain at -50°C is 0.70 to 20, A film having a thermal conductivity of 0.10 to 5.0 W / (m·K) at 25°C.

7. The film according to claim 6, wherein the (SA) binder resin contains (SA1-2) silicone resin and / or polysiloxane.

8. The silicone resin is a resin whose main skeleton is a bifunctional organosilane unit having two organic groups on a silicon atom and the silicon atom bonded to two oxygen atoms, In the silicone resin, the content ratio of difunctional organosilane units to the total organosilane units is 50 mol% or more and 100 mol% or less. The polysiloxane is a resin whose main skeleton is a trifunctional organosilane unit in which one organic group is located on a silicon atom and the silicon atom is bonded to three oxygen atoms, The film according to claim 7, wherein the polysiloxane has a content ratio of trifunctional organosilane units to the total organosilane units of 50 mol% or more and 100 mol% or less.

9. A film according to any one of claims 1 to 8, satisfying at least one of the following conditions (S1a), (S2a), (S3a), (S1b), (S2b), and (S3b). (S1a) The boron content in the film is 5.0% by mass or less. (S2a) The phosphorus content in the film is 1,000 ppm by mass or less. (S3a) The total content of chlorine and bromine elements in the film is 1,000 ppm by mass or less. (S1b) The total content of boron-containing ions in the film is 5.0% by mass or less. (S2b) The total content of phosphorus-containing ions in the film is 5,000 ppm by mass or less. (S3b) The total content of chloride ions and bromide ions in the film is 1,000 ppm by mass or less.

10. A film according to any one of claims 1 to 8, satisfying at least one of the following conditions (S4a) and (S4b). (S4a) Platinum element content in the film is 1,000 ppm by mass or less. (S4b) The total content of platinum-containing ions in the film is 5,000 ppm by mass or less.

11. A film according to any one of claims 1 to 8, satisfying 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 ppm by mass or less. (S5b) The total content of cyclic silicone compounds in the film is 1,000 ppm by mass or less.

12. The film according to any one of claims 1 to 8, wherein the (SA) binder resin contains a resin that includes a silicone structure and / or a siloxane structure in the structural units of the (SA1) resin.

13. The film according to claim 12, wherein the content ratio of the aliphatic group to the total of the aliphatic groups and aromatic groups bonded to the silicon atoms in the silicone structure and / or the siloxane structure is 80 to 100 mol%.

14. (SC) Contains an amine compound or a compound having a structure derived from an amine compound (hereinafter referred to as "(SC) compound"), The film according to any one of claims 1 to 8, wherein the (SC) compound contains a compound having a (SC1) silicone structure and / or siloxane structure, and having at least two alkylene groups bonded to silicon atoms in the silicone structure and / or siloxane structure.

15. The film according to any one of claims 1 to 8, wherein the elastic modulus of the film at 25°C is 0.010 to 1.0 MPa.

16. The film according to any one of claims 1 to 8, wherein the film is a cured product of the composition.

17. A laminate comprising a base member, a film according to any one of claims 1 to 8, and a ceramic dielectric member in this order, A laminate in which the thermal expansion coefficients of the base member and the ceramic dielectric member are different.

18. The laminate according to claim 17, wherein the difference in thermal expansion coefficients between the base member and the ceramic dielectric member is 1.0 to 30 ppm / K.

19. A plasma processing apparatus comprising a plasma source and the laminate described in claim 17.

20. A method for manufacturing a laminate, comprising the steps of arranging a base member, arranging a film according to any one of claims 1 to 8, and arranging a ceramic dielectric member.