Heat-resistant release film

Abstract

This heat-resistant release film includes a base material layer (a) (10) and a resin layer (b) (20) containing an olefin-based polymer (A) having a crosslinkable group.

Description

Heat-resistant release film

[0001] This invention relates to a heat-resistant release film (hereinafter also referred to as a release film).

[0002] For example, release films are used in semiconductor manufacturing processes. Examples of technologies related to release films include those described in Patent Documents 1 and 2.

[0003] Patent Document 1 discloses a single-layer heat-resistant release film and a method for manufacturing a heat-resistant release film, which can be suitably used in the molding of thermosetting resins and the manufacture of electronic components, and which has excellent heat resistance, environmental suitability, and workability, and which does not undergo delamination in an essential way. The objective is to provide a single-layer heat-resistant release film and a method for manufacturing a heat-resistant release film, characterized in that it contains 98 to 60% by mass of a styrene-based polymer having a syndiotactic structure and 2 to 40% by mass of an elastomer, and has a degree of crystallinity of 40% or more.

[0004] Patent Document 2 addresses the objective of providing a sheet that can more reliably cope with further increases in the expected thermocompression temperature, and describes a heat-resistant release sheet that is placed between the object to be pressed and the heat-pressure head during thermocompression of the object by the heat-pressure head to prevent the object to be pressed and the heat-pressure head from sticking together, wherein the surface hardness at 300°C is given by formula: A ３００ (%) = (d ３００ / t ０ The degree of indentation A is given by ) × 100. ３００ A heat-resistant release sheet is disclosed that is indicated as 15% or less. However, t ０ This is the thickness of the heat-resistant release sheet at room temperature (20°C). ３００ This is the amount of indentation of the needle probe into the heat-resistant release sheet at 300°C, as evaluated by thermomechanical analysis (TMA) based on specific measurement conditions.

[0005] Japanese Patent Publication No. 2017-115056 Japanese Patent Publication No. 2020-059273

[0006] In conventional release films, it has been difficult to achieve both release properties and heat resistance under high-temperature environments. The present invention provides a release film that can maintain release properties while having heat resistance under high-temperature environments.

[0007] According to the present invention, there is provided a heat-resistant release film as described below. [1] A heat-resistant release film comprising a base material layer (a) and a resin layer (b) containing an olefin polymer (A) having a crosslinkable group. [2] The heat-resistant release film according to [1] above, wherein the base material layer (a) contains one or more selected from the group consisting of polyimide resin, modified polyimide resin, polyamideimide resin, polyetheretherketone resin, polyaryletherketone resin, silicone resin, and modified silicone resin. [3] The heat-resistant release film according to [1] or [2] above, wherein the resin layer (b) further contains a complex (B), and the complex (B) contains a metal atom and a ligand. [4] The heat-resistant release film according to [3] above, wherein the ligand has a total of two or more of one or more selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds, and has an organosiloxane structure. [5] The heat-resistant release film according to [4] above, wherein the ligand contains a ligand represented by the following formula (L1). [In the formula (L1), n represents an integer of 0 or more, and R １１ to R １６ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms, and R ２１ to R ２４ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or an organosiloxane group having 1 to 20 silicon atoms, X each independently represents a direct bond or an alkylene group having 1 to 4 carbon atoms, R １１ and R １２ , R １１ and R １３ , R １２ and R １３ , R １４ and R１５ , R １４ and R １６ , R １５ and R １６ , R ２１ and R ２２ , R ２１ and R ２３ , R ２１ and R ２４ , R ２２ and R ２３ , R ２２ and R ２４ , or R ２３ and R ２４ The members may be bonded to each other to form a monocycle or polycycle. ] [6] The heat-resistant release film according to any one of [3] to [5], wherein the content of the complex (B) in the resin layer (b) is 0.0001 parts by mass or more and 5 parts by mass or less, when the content of the olefin polymer (A) in the resin layer (b) is 100 parts by mass. [7] The heat-resistant release film according to any one of [1] to [6], wherein the resin layer (b) further comprises a hydrosilylation agent (C) having a hydrosilyl group and a siloxane structure. [8] The heat-resistant release film according to [7], wherein the hydrosilylation agent (C) comprises a compound represented by the following formula (H1). [In the above formula (H1), m １ represents a positive integer, and m ２ R represents a non-negative integer, ３１ ~R ３９Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or an organosiloxane group having 1 to 20 silicon atoms. [9] The heat-resistant release film according to [7] or [8], wherein the content of the hydrosilylated agent (C) in the resin layer (b) is 0.01 parts by mass or more and 10 parts by mass or less when the content of the olefin polymer (A) in the resin layer (b) is 100 parts by mass.

[10] The heat-resistant release film according to any one of [1] to [9], wherein the content of fluorine atoms in the resin layer (b) is 50 parts by mass or less when the content of the olefin polymer (A) in the resin layer (b) is 100 parts by mass.

[11] The heat-resistant release film according to any one of [1] to

[10] , wherein the olefin polymer (A) comprises a cyclic olefin copolymer (A1) having a crosslinkable group.

[12] The heat-resistant release film according to

[11] , wherein the cyclic olefin copolymer (A1) comprises a repeating unit (a1) represented by the following formula (I), one or more repeating units (a2) selected from the group consisting of a repeating unit represented by the following formula (II), a repeating unit represented by the following formula (III), and a repeating unit represented by the following formula (IV), and a repeating unit (a3) ​​represented by the following formula (V). [In the above formula (I), R ３００ This represents a hydrogen atom or a linear or branched alkyl group having 1 to 29 carbon atoms. [In formula (II) above, u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, R ６１ ~R ７６ , R ａ１ , and R ｂ１ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R １０２ and R １０３ Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R７５ and R ７６ These may be bonded to each other to form a monocycle or polycycle. [In formula (III) above, t represents an integer from 0 to 10, u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, R ６１ ~R ７６ , R ａ１ , and R ｂ１ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R １０４ R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ７５ and R ７６ These may be bonded to each other to form a monocycle or polycycle. [In formula (IV) above, u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, R ６１ ~R ７６ , R ａ１ , and R ｂ１ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ and R ７６ These may be bonded to each other to form a monocycle or polycycle. [In the above formula (V), u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, R ６１ ~R ７８ , R ａ１ , and R ｂ１ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ７５ and R ７６ , R ７６ and R ７７ , or R ７７ and R ７８These may be bonded to each other to form a monocycle or polycycle. ]

[13] The heat-resistant release film according to

[12] , wherein the olefin constituting the repeating unit (a1) contains ethylene.

[14] The cyclic non-conjugated diene constituting the repeating unit (a2) is 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 ２，５ 1. ７，１０ A heat-resistant release film according to

[12] or

[13] , comprising one or more selected from the group consisting of ]-3-dodecene and 5-allyl-2-norbornene.

[15] The cyclic olefin constituting the repeating unit (a3) ​​is tetracyclo[4.4.0.1 ２，５ 1. ７，１０ A heat-resistant release film according to any one of

[12] to

[14] , comprising one or more selected from the group consisting of ]-3-dodecene and bicyclo[2.2.1]-2-heptene.

[16] A heat-resistant release film according to any one of [1] to

[15] , wherein the resin layer (b) further comprises a reaction inhibitor (D).

[17] A heat-resistant release film according to

[16] , wherein the content of the reaction inhibitor (D) in the resin layer (b) is 10 parts by mass or less, when the content of the olefin polymer (A) in the resin layer (b) is 100 parts by mass.

[18] A heat-resistant release film according to any one of [1] to

[17] , wherein the resin layer (b) is in an uncured or semi-cured state.

[19] A heat-resistant release film according to any one of [1] to

[18] , wherein the thickness of the base layer (a) is 1 μm or more and 100 μm or less.

[20] The heat-resistant release film according to any one of [1] to

[19] , wherein the thickness of the resin layer (b) is 0.1 μm or more and 50 μm or less.

[21] Peel strength P according to the following (Method 1) ０A heat-resistant release film according to any one of [1] to

[20] above, wherein the strength is 5.0 N / 19 mm or less. (Method 1) A 30 mm x 130 mm test piece is prepared from the heat-resistant release film. Then, an adhesive tape with a thickness of 25 μm and a width of 19 mm is attached to the surface of the test piece on the resin layer (b) side. Then, using a peel strength measuring device, the 90° peel strength is measured by the tape peel method under the conditions of 25°C, 80% RH or less, load cell 5 kgf, crosshead speed 300 mm / min, and chart speed 30 mm / min.

[22] Peel strength P according to the following (Method 2) １ A heat-resistant release film according to any one of [1] to

[21] above, wherein the coefficient of heat is 5.0 N / 19 mm or less. (Method 2) A 30 mm x 130 mm test piece is prepared from the heat-resistant release film. A structure is then prepared by sandwiching the test piece between two 0.3 mm thick SUS plates. The structure is then heated at 350°C for 1 minute using a small test press. The structure is then cooled to 30°C by leaving it sandwiched in the small test press set to 30°C for 3 minutes. The test piece is then removed from the structure. A 25 μm thick, 19 mm wide adhesive tape is then attached to the surface of the test piece on the resin layer (b) side. The 90° peel strength is then measured using a peel strength measuring device by the tape peel method at 25°C, 80% RH or less, load cell 5 kgf, crosshead speed 300 mm / min, and chart speed 30 mm / min.

[23] A heat-resistant release film used in semiconductor processes, as described in any of [1] to

[22] above.

[0008] According to the present invention, it is possible to provide a release film that maintains release properties while having heat resistance in high-temperature environments.

[0009] This is a schematic cross-sectional view showing an example of the structure of the release film according to this embodiment.

[0010] The present invention will be described below based on embodiments. In these embodiments, unless otherwise specified, "A to B" indicating a numerical range means A or greater and B or less. Furthermore, when a numerical range is described in steps, the upper and lower limits of each numerical range can be arbitrarily combined. In addition, the description "A and / or B" is a concept that includes the case of A, the case of B, and the case of both A and B. In the notation of groups (atomic groups) in this specification, the notation that does not specify whether it is substituted or unsubstituted includes both those that do not contain substituents and those that contain substituents. For example, "alkyl group" includes not only alkyl groups that do not contain substituents (unsubstituted alkyl groups) but also alkyl groups that contain substituents (substituted alkyl groups). In this specification, the notation "(meth)acrylic" represents a concept that includes both acrylic and methacrylic. The same applies to similar notations such as "(meth)acrylate". Furthermore, each monomer constituting the "olefin polymer (A) having a crosslinkable group" in this specification may be a monomer obtained from fossil raw materials, a monomer obtained from animal or plant raw materials, or a monomer obtained from raw materials obtained by chemical recycling.

[0011] This embodiment will be described below with reference to the drawings as appropriate. In all drawings, similar components are denoted by the same reference numerals, and their descriptions are omitted as appropriate. Also, the drawings are schematic diagrams and do not correspond to the actual dimensional ratios.

[0012] [Release Film] The release film of this embodiment comprises a base layer (a) and a resin layer (b) containing an olefin polymer (A) having crosslinkable groups. The release film of this embodiment, having the above configuration, can maintain release properties while having heat resistance in high-temperature environments.

[0013] The reason why the effects of this embodiment are obtained is not entirely clear, but the following reasons can be inferred. The release film of this embodiment is thought to be able to maintain release properties while having heat resistance in high-temperature environments of 350°C or higher by introducing crosslinking groups into an olefin polymer (A) that has release properties to improve the heat resistance of the resin layer (b).

[0014] The release film of this embodiment includes a base layer (a) and a resin layer (b) containing the film of this embodiment. That is, the release film has a resin layer (b) on at least one side of the base layer (a). From the viewpoint of reducing warping of the release film, the release film preferably has resin layers (b) on both sides of the base layer (a). In this case, the release film has a base layer (a) between the two resin layers (b). Also, when the release film has two resin layers (b), the release film may have an intermediate layer between the resin layer (b) and the base layer (a). In this case, the release film may have each layer in the order of, for example, resin layer (b); intermediate layer (c); base layer (a); intermediate layer (c); resin layer (b); resin layer (b); resin layer (b); base layer (a); intermediate layer (c); resin layer (b); or resin layer (b); intermediate layer (c); base layer (a); resin layer (b).

[0015] Next, the specific structure of the release film of this embodiment will be described with reference to the figures. Figure 1 schematically shows an example of the layer configuration of the release film (release film 200) of this embodiment. Figure 2 schematically shows an example of the layer configuration when the release film (release film 200) of Figure 1 includes an intermediate layer (c) which will be described later.

[0016] The release film 200 in Figure 1 comprises a base layer (a) 10 and a resin layer (b) 20 in that order. In other words, the release film 200 comprises a base layer (a) 10 and a resin layer (b) 20 on one side of the base layer (a) 10. The release film 200 in Figure 2 comprises a base layer (a) 10, an intermediate layer (c) 30, and a resin layer (b) 20 in that order. In other words, the release film 200 has an intermediate layer (c) 30 between the base layer (a) 10 and the resin layer (b) 20.

[0017] The overall thickness of the release film in this embodiment is preferably 1 μm to 150 μm, more preferably 2 μm to 130 μm, even more preferably 4 μm to 100 μm, even more preferably 6 μm to 80 μm, even more preferably 8 μm to 60 μm, and even more preferably 10 μm to 50 μm, from the viewpoint of improving the balance of mechanical properties, heat transfer properties, and handling properties.

[0018] Examples of the release film shape in this embodiment include film-like or sheet-like forms.

[0019] <Applications of the release film> The release film of this embodiment can maintain its release properties while having heat resistance in high-temperature environments, so the applications of the film of this embodiment are not particularly limited and can be applied to a variety of applications. Examples of applications for the release film of this embodiment include semiconductor process applications; sintering process applications for power semiconductor packaging; and packaging process applications for laminated substrates.

[0020] In this embodiment, the temperature in the high-temperature environment is, for example, 100°C to 380°C, preferably 120°C to 380°C, more preferably 150°C to 350°C, even more preferably 200°C to 350°C, even more preferably 250°C to 350°C, and even more preferably 300°C to 350°C.

[0021] The release film of this embodiment can maintain release properties while having heat resistance in high-temperature environments, and is therefore preferably used in semiconductor manufacturing processes. In this specification, semiconductor manufacturing processes refer to processes for manufacturing semiconductor chips, semiconductor packages, printed circuit boards, or semiconductor devices comprising them. The film of this embodiment has an improved balance of release properties and heat resistance, and is therefore preferably used in the mounting process in semiconductor manufacturing processes, and more preferably as a heat-resistant release film for protecting chips and preventing adhesive contamination during thermocompression bonding in the memory chip three-dimensional integration process.

[0022] <Method for Manufacturing Release Film> Examples of methods for manufacturing the laminated film in this embodiment include lamination and coating methods. The method for manufacturing the laminated film can be selected according to the type of base material layer (a), the type of resin layer (b), etc. The method for manufacturing the release film can be, for example, the method described in the example.

[0023] Next, specific examples of the components of the release film in this embodiment will be given.

[0024] The release film of this embodiment comprises a base layer (a) and a resin layer (b). The release film may also comprise layers other than the base layer (a) and the resin layer (b). Examples of layers other than the base layer (a) and the resin layer (b) include an intermediate layer (c), an adhesive layer, an unevenness absorption layer, an impact absorption layer, a heat transfer layer, a coating layer, and the like, which will be described later.

[0025] <Base layer (a)> Base layer (a) is the layer that is heated by the heat source (the side that comes into contact with the heating and pressing head) when electronic components are joined together by heat and pressure. By providing base layer (a), the mechanical properties of the release film are improved, and the transportability and handling of the release film can be improved.

[0026] Examples of the base layer (a) include heat-resistant resin films and metal foils. Examples of resins constituting the heat-resistant resin film include polyimide resin, modified polyimide resin, polyamide-imide resin, polyetheretherketone resin, polyaryletherketone resin, silicone resin, polyetherketone resin, polyetherketoneketone resin, polyetheretherketoneketone resin, polyetherketoneetherketoneketone resin, polyamide resin, polyester resin, polyetherimide resin, polycarbonate resin, modified polyphenylene ether resin, polyacetal resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, liquid crystal polymer, vinylidene chloride resin, polybenzimidazole resin, polybenzoxazole resin, polymethylpentene resin, or resins modified from these resins. Examples of metals constituting the metal foil include copper, aluminum, nickel, stainless steel, titanium, silver, gold, and molybdenum.

[0027] The base layer (a) preferably contains a heat-resistant resin, more preferably one or more selected from the group consisting of polyimide resin, modified polyimide resin, polyamide-imide resin, polyetheretherketone, polyaryletherketone, and silicone resin, and even more preferably a polyimide resin.

[0028] The base layer (a) may be a single layer or a layer consisting of two or more layers.

[0029] From the viewpoint of improving film properties, the thickness of the substrate layer (a) is preferably 1 μm or more and 100 μm or less, more preferably 2 μm or more and 50 μm or less, even more preferably 3 μm or more and 40 μm or less, even more preferably 4 μm or more and 35 μm or less, and even more preferably 5 μm or more and 30 μm or less.

[0030] The substrate layer (a) may be surface-treated to improve its adhesion to other layers. Examples of surface treatments include corona treatment, plasma treatment, undercoat treatment, and primer coating.

[0031] <Resin layer (b)> Resin layer (b) is a layer that is positioned opposite to the electronic components when joining them together by heat and pressure (the layer positioned on the electronic component side), and is provided to peel off the release film from the electronic components after the electronic components have been heat and pressure-bonded.

[0032] The resin layer (b) may be a single layer or a layer consisting of two or more layers.

[0033] From the viewpoint of improving mold release properties, the thickness of the resin layer (b) is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 40 μm, even more preferably 1 μm to 30 μm, even more preferably 2 μm to 25 μm, and even more preferably 3 μm to 20 μm.

[0034] The resin layer (b) may be surface-treated to improve its adhesion to other layers. Examples of surface treatments include corona treatment, plasma treatment, undercoat treatment, and primer coat treatment.

[0035] Next, the components of the resin layer (b) will be explained with specific examples. The resin layer (b) contains an olefin polymer (A) having crosslinkable groups (hereinafter also referred to as polymer (A)). The resin layer (b) may be composed of polymer (A), or it may contain components other than polymer (A). Other components of the resin layer (b) may include, for example, a complex (B) described later, a hydrosilylation agent (C), a reaction inhibitor (D), a radical initiator, an olefin polymer other than polymer (A), an aromatic polymer, a fluororesin, etc. Each component will be explained separately below.

[0036] <Complex (B)> The resin layer (b) preferably further contains complex (B) from the viewpoint of maintaining release properties while having heat resistance in high-temperature environments. Furthermore, from the viewpoint of obtaining a film with an improved balance of release properties and heat resistance, complex (B) contains a metal atom (B1) and a ligand (B2).

[0037] Examples of metal atoms (B1) include platinum group atoms (b1) and base metal atoms (b2), which will be described later. Examples of base metal atoms (b2) include iron, cobalt, nickel, and manganese. When complex (B) contains a base metal atom (b2), complex (B) may also contain a combination of a base metal atom (b2) and a ligand (B3) instead of a combination of a platinum group atom (b1) and a ligand (B2). In this case, the ligand (B3) is a compound appropriately selected in accordance with the base metal atom (b2).

[0038] Complex (B) includes, for example, a catalyst used in a hydrosilylation reaction. In this case, complex (B) is an addition catalyst. Such an addition catalyst promotes the addition reaction of the hydrosilyl group (SiH group) of the hydrosilylation agent (C), described later, to the carbon-carbon double bond in polymer (A) (polymer (A1), described later). Examples of such addition catalysts include those made of platinum group elements such as platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Examples of addition catalysts include those made of group 8 metals, group 8 metal complexes, and group 8 metal compounds of the periodic table. The addition catalyst may also be a base metal catalyst. Examples of base metal catalysts include iron-based catalysts, cobalt-based catalysts, and nickel-based catalysts.

[0039] Platinum group atoms (b1) are atoms of the platinum group elements. Examples of platinum group atoms (b1) include platinum atoms, palladium atoms, rhodium atoms, ruthenium atoms, osmium atoms, iridium atoms, etc. From the viewpoint of further improving the balance between release properties and heat resistance, the platinum group atoms (b1) preferably include one or more selected from the group consisting of platinum atoms, palladium atoms, rhodium atoms, ruthenium atoms, osmium atoms, and iridium atoms, more preferably include one or more selected from the group consisting of platinum atoms, palladium atoms, rhodium atoms, and ruthenium atoms, and even more preferably include platinum atoms.

[0040] Ligand (B2) preferably has a total of two or more of one or more types selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds, from the viewpoint of further improving the balance between release properties and heat resistance. Ligand (B2) may have a total of two or more carbon-carbon double bonds, a total of two or more carbon-carbon triple bonds, or one or more carbon-carbon double bonds and one or more carbon-carbon triple bonds.

[0041] Furthermore, the ligand (B2) preferably has an organosiloxane structure from the viewpoint of further improving the balance between release properties and heat resistance. An organosiloxane structure refers to a structure in which various organic groups are located on the Si atoms of a siloxane polymer having a repeating (-Si-O-) bond structure.

[0042] When ligand (B2) has a total of two or more of one or more types selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds, and has an organosiloxane structure, it is thought that in the resin layer (b), the catalytic function of complex (B) having a predetermined structure is exerted to promote crosslinking of polymer (A), and the organosiloxane structure of complex (B) imparts release properties to the resin layer (b). In other words, it is thought that, due to the synergistic effect of polymer (A) and complex (B), the crosslinking of polymer (A) proceeds appropriately by the catalytic action of complex (B), and the release properties are improved by complex (B), thereby obtaining a release film with an improved balance of release properties and heat resistance.

[0043] The ligand (B2) preferably contains a ligand represented by the following formula (L1) from the viewpoint of further improving the performance balance between mold release properties and heat resistance. In this case, the complex (B) contains a ligand represented by the following formula (L1).

[0044]

[0045] In formula (L1), n represents an integer of 0 or more. Also, R １１ ~R １６ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms. Also, R ２１ ~R ２４ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 2l carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or an organosiloxane group having 1 to 20 silicon atoms. Also, X each independently represents a direct bond or an alkylene group having 1 to 4 carbon atoms. Also, R １１ and R １２ , R １１ and R １３ , R １２ and R １３ , R １４ and R １５ , R １４ and R １６ , R １５ and R １６ , R ２１ and R ２２ , R ２１ and R ２３ , R ２１ and R ２４ , R ２２ and R ２３ , R ２２ and R ２４ , or R ２３ and R ２４ may be bonded to each other to form a monocyclic or polycyclic ring.

[0046] Examples of organosiloxane groups having 1 to 20 silicon atoms include siloxy groups and modified siloxy groups. Organosiloxane groups having 1 to 20 silicon atoms include organosiloxane groups in which hydrogen atoms in the organosiloxane group are partially substituted with halogen atoms such as fluorine. When the ligand represented by formula (L1) has an organosiloxane group having 1 to 20 silicon atoms, the ligand represented by formula (L1) may have a branched organosiloxane structure.

[0047] In formula (L1), n ​​is preferably an integer of 5 or less, more preferably an integer of 3 or less, and even more preferably 2 or less, from the viewpoint of further improving the balance between release properties and heat resistance.

[0048] R in equation (L1) １１ ~R １６ Each of these components is preferably one or more selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, and an organosiloxane group having 1 to 20 silicon atoms, more preferably one or more selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a siloxy group, a modified siloxy group, and a fluorinated alkyl group, and even more preferably a hydrogen atom.

[0049] R in equation (L1) ２１ ~R ２４ Each of these groups is preferably one or more selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an alkyl halide having 1 to 20 carbon atoms, and an organosiloxane group having 1 to 20 silicon atoms, more preferably one or more selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and a phenyl group, and even more preferably a methyl group.

[0050] In formula (L1), each X is independently selected from the group consisting of direct bonds and alkylene groups having 1 to 4 carbon atoms, preferably one or more selected from the group consisting of direct bonds, methylene groups, and ethylene groups, and even more preferably a direct bond, from the viewpoint of further improving the balance of release properties and heat resistance.

[0051] In complex (B), the combination of metal atom (B1) and ligand (B2) is not limited to those described above. Examples of complex (B) other than the above combination of metal atom (B1) and ligand (B2) include hexachloroplatin(IV) acid, tetrachloroplatin(II) acid, chlorotris(triphenylphosphine)rhodium(I), and pentamethylcyclopentadienyltris(acetonitrile)ruthenium(II)hexafluorophosphate. When complex (B) includes complex (B) other than the combination of metal atom (B1) and ligand (B2), the resin composition of this embodiment further includes a hydrosilylating agent (C) described later.

[0052] From the viewpoint of improving release properties, the content of complex (B) in the resin layer (b) is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, even more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, and even more preferably 0.015 parts by mass or more, when the content of polymer (A) in the resin layer (b) is 100 parts by mass. From the viewpoint of reducing the decrease in heat resistance due to embrittlement of the release film, the content of complex (B) in the resin layer (b) is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, even more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.8 parts by mass or less, even more preferably 0.6 parts by mass or less, even more preferably 0.5 parts by mass or less, and even more preferably 0.4 parts by mass or less, when the content of polymer (A) in the resin layer (b) is 100 parts by mass. From the viewpoint of further improving the balance between release properties and heat resistance, the content of complex (B) in the resin layer (b) is preferably 0.0001 parts by mass or more and 5 parts by mass or less, more preferably 0.0001 parts by mass or more and 4 parts by mass or less, more preferably 0.0001 parts by mass or more and 3 parts by mass or less, even more preferably 0.0001 parts by mass or more and 2 parts by mass or less, even more preferably 0.0001 parts by mass or more and 1 part by mass or less, even more preferably 0.001 parts by mass or more and 0.8 parts by mass or less, even more preferably 0.005 parts by mass or more and 0.6 parts by mass or less, even more preferably 0.01 parts by mass or more and 0.5 parts by mass or less, and even more preferably 0.015 parts by mass or more and 0.4 parts by mass or less, when the content of polymer (A) in the resin layer (b) is 100 parts by mass.

[0053] From the viewpoint of further improving the balance between release properties and heat resistance, the content of complex (B) in the resin layer (b) is preferably 0.0001% to 5% by mass, more preferably 0.0001% to 4% by mass, even more preferably 0.0001% to 3% by mass, even more preferably 0.0001% to 2% by mass, even more preferably 0.0001% to 1% by mass, even more preferably 0.0001% to 0.8% by mass, even more preferably 0.005% to 0.6% by mass, even more preferably 0.01% to 0.5% by mass, and even more preferably 0.015% to 0.4% by mass.

[0054] <Hydrosilylation agent (C)> The resin layer (b) preferably further contains a hydrosilylation agent (C) from the viewpoint of further improving the balance between release properties and heat resistance. The hydrosilylation agent (C) is a compound that acts as a crosslinking agent that reacts with the polymer (A). The hydrosilylation agent (C) has a hydrosilyl group (SiH group). That is, the hydrosilylation agent (C) has a hydrogen atom directly bonded to a silicon atom. The molecular structure of the hydrosilylation agent (C) is not particularly limited as long as it has a hydrosilyl group. Examples of molecular structures of the hydrosilylation agent (C) include linear, branched, cyclic, and three-dimensional network structures.

[0055] From the viewpoint of further improving the balance between release properties and heat resistance, the hydrosilylation agent (C) preferably has two or more hydrosilyl groups, and more preferably has three or more hydrosilyl groups.

[0056] The hydrosilylation agent (C) preferably has a hydrosilyl group and a siloxane structure, from the viewpoint of further improving the balance between release properties and heat resistance. The siloxane structure refers to a repeating structure of (-Si-O-) bonds.

[0057] The hydrosilylation agent (C) preferably includes a compound represented by the following formula (H1) from the viewpoint of further improving the balance between release properties and heat resistance.

[0058]

[0059] In equation (H1), m １ represents a positive integer. Also, m ２ This represents a non-negative integer. Also, R ３１ ~R ３９ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms, or an organosiloxane group having 1 to 20 silicon atoms.

[0060] Examples of organosiloxane groups having 1 to 20 silicon atoms include siloxy groups and modified siloxy groups. Organosiloxane groups having 1 to 20 silicon atoms include organosiloxane groups in which hydrogen atoms in the organosiloxane group are partially substituted with halogen atoms such as fluorine. When the compound represented by formula (H1) has an organosiloxane group having 1 to 20 silicon atoms, the compound represented by formula (H1) may have a branched organosiloxane structure.

[0061] m in equation (H1) １ From the viewpoint of further improving the balance between release properties and heat resistance, it is preferably a positive integer, more preferably an integer between 2 and 1,000, and even more preferably an integer between 3 and 500.

[0062] m in equation (H1) ２ From the viewpoint of further improving the balance between release properties and heat resistance, it is preferably an integer of 0 or more, more preferably an integer of 1 to 1,000, and even more preferably an integer of 2 to 500.

[0063] m in equation (H1) １ +m ２From the viewpoint of further improving the balance between release properties and heat resistance, it is preferably an integer of 1 or more, more preferably an integer of 3 to 2,000, and even more preferably an integer of 5 to 1,000.

[0064] R in equation (H1) ３１ ~R ３９ Each of these components is, independently of the viewpoint of further improving the balance between release properties and heat resistance, preferably one or more selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an alkyl halide having 1 to 20 carbon atoms, and an organosiloxane group having 1 to 20 silicon atoms; more preferably one or more selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group; and even more preferably one or more selected from the group consisting of a hydrogen atom and a methyl group.

[0065] From the viewpoint of improving release properties, the content of the hydrosilylation agent (C) in the resin layer (b) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.2 parts by mass or more, and even more preferably 0.5 parts by mass or more, when the content of the polymer (A) in the resin layer (b) is 100 parts by mass. From the viewpoint of reducing appearance defects or quality defects due to whitening of the release film, the content of the hydrosilylation agent (C) in the resin layer (b) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 6 parts by mass or less, even more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, when the content of the polymer (A) in the resin layer (b) is 100 parts by mass. From the viewpoint of improving release properties and reducing appearance defects or quality defects due to whitening of the release film, the content of the hydrosilylation agent (C) in the resin layer (b) is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 8 parts by mass or less, even more preferably 0.1 parts by mass or more and 6 parts by mass or less, even more preferably 0.2 parts by mass or more and 4 parts by mass or less, and even more preferably 0.5 parts by mass or more and 3 parts by mass or less.

[0066] From the viewpoint of further improving the balance between release properties and heat resistance, the content of the hydrosilylation agent (C) in the resin layer (b) is preferably 10 parts by mass or more and 2000 parts by mass or less, more preferably 20 parts by mass or more and 2000 parts by mass or less, even more preferably 30 parts by mass or more and 2000 parts by mass or less, even more preferably 50 parts by mass or more and 1800 parts by mass or less, even more preferably 100 parts by mass or more and 1600 parts by mass or less, and even more preferably 500 parts by mass or more and 1500 parts by mass or less.

[0067] From the viewpoint of further improving the balance between release properties and heat resistance, the content of the hydrosilylation agent (C) in the resin layer (b) is preferably 0.01% to 10% by mass, more preferably 0.05% to 5.0% by mass, even more preferably 0.1% to 4.0% by mass, and even more preferably 0.3% to 2.5% by mass, when the total amount of solids in the resin layer (b) (total amount of components remaining as solids when cured) is taken as 100% by mass.

[0068] <Olefin polymer (A) having crosslinkable groups> The resin layer (b) contains polymer (A) from the viewpoint of maintaining release properties while having heat resistance in high-temperature environments. Polymer (A) can be used without particular limitations as long as it has crosslinkable groups and contains repeating units derived from olefins. Polymer (A) may be a homopolymer or a copolymer.

[0069] Polymer (A) has crosslinkable groups from the viewpoint of improving heat resistance. The crosslinkable groups include, for example, one or more selected from the group consisting of vinyl groups; vinylidene groups; vinylene groups; vinyl groups substituted with alkyl groups, phenyl groups or alkylphenyl groups; vinylidene groups substituted with alkyl groups, phenyl groups or alkylphenyl groups; vinylene groups substituted with alkyl groups, phenyl groups or alkylphenyl groups; maleimide groups; thiol groups; thienyl groups; silyl groups; epoxy groups; oxazoline groups; (meth)acrylic groups; carboxyl groups; and hydrosilyl groups. Polymer (A) preferably contains vinyl groups from the viewpoint of obtaining a film with a better balance of release properties and heat resistance.

[0070] Examples of polymers (A) include cyclic olefin copolymers having crosslinkable groups (A1) (hereinafter also referred to as copolymer (A1)), cyclic olefin polymers having crosslinkable groups (A2) (hereinafter also referred to as polymer (A2)), olefin homopolymers having crosslinkable groups, and olefin copolymers having crosslinkable groups.

[0071] Examples of polymer (A2) include ring-opening polymers of cyclic olefins and addition polymers of cyclic olefins having crosslinkable groups. Polymer (A2) may have, for example, a cyclic structure with four or more membered rings, or an alicyclic structure.

[0072] Examples of olefin-based homopolymers having crosslinkable groups include polydivinylbenzene, polybutadiene, and polydicyclopentadiene (dicyclopentadiene resin). Examples of olefin-based copolymers having crosslinkable groups include polydivinylbenzene with introduced crosslinkable groups, polybutadiene with introduced crosslinkable groups, polydicyclopentadiene with introduced crosslinkable groups, polystyrene-polybutadiene-polystyrene block copolymer with introduced crosslinkable groups, polystyrene-polyethylene-polybutadiene-polystyrene block copolymer with introduced crosslinkable groups, styrene-butadiene copolymer with introduced crosslinkable groups, and polyacetylene with introduced crosslinkable groups.

[0073] Polymer (A) preferably includes a cyclic olefin polymer from the viewpoint of obtaining a film with a better balance of release properties and heat resistance. Examples of cyclic olefin polymers include copolymer (A1) and polymer (A2).

[0074] <Cyclic olefin copolymer (A1) having crosslinkable groups> Polymer (A) will be described in detail below using copolymer (A1), but polymer (A) in this embodiment is not limited to the following embodiments.

[0075] The resin layer (b) contains copolymer (A1) so that it can maintain release properties while having heat resistance in high-temperature environments. Examples of copolymer (A1) include thermosetting cyclic olefin copolymers and photocurable cyclic olefin copolymers. In addition, copolymer (A1) can be used without particular limitations as long as it is a copolymer that contains repeating units derived from cyclic olefins.

[0076] The copolymer (A1) has crosslinkable groups, from the viewpoint of maintaining release properties while having heat resistance in high-temperature environments. The crosslinkable groups include, for example, one or more selected from the group consisting of vinyl groups; vinylidene groups; vinylene groups; vinyl groups substituted with alkyl groups, phenyl groups or alkylphenyl groups; vinylidene groups substituted with alkyl groups, phenyl groups or alkylphenyl groups; vinylene groups substituted with alkyl groups, phenyl groups or alkylphenyl groups; maleimide groups; thiol groups; thienyl groups; silyl groups; epoxy groups; oxazoline groups; (meth)acrylic groups; carboxyl groups; and hydrosilyl groups. From the viewpoint of further improving the balance between release properties and heat resistance, the copolymer (A1) preferably contains vinyl groups.

[0077] The copolymer (A1) preferably has a norbornene skeleton from the viewpoint of further improving the balance between release properties and heat resistance. The copolymer (A1) includes, for example, one or more selected from the group consisting of repeating units (a2) and (a3) ​​described later.

[0078] (Composition of copolymer (A1)) Next, the repeating units of copolymer (A1) will be explained.

[0079] The copolymer (A1) includes repeating units (a1), repeating units (a2), and repeating units (a3) ​​from the viewpoint of further improving the balance between release properties and heat resistance. Repeating unit (a1) is a repeating unit represented by the following formula (I). In other words, repeating unit (a1) is a repeating unit derived from one or more olefins. Repeating unit (a2) is one or more repeating units selected from the group consisting of repeating units represented by the following formula (II), repeating units represented by the following formula (III), and repeating units represented by the following formula (IV). In other words, repeating unit (a2) is a repeating unit derived from one or more cyclic non-conjugated dienes. Repeating unit (a3) ​​is a repeating unit represented by the following formula (V). In other words, repeating unit (a3) ​​is a repeating unit derived from one or more cyclic olefins.

[0080] In the following, the repeating unit represented by formula (II) will also be called repeating unit (a22). The repeating unit represented by formula (III) will also be called repeating unit (a23). The repeating unit represented by formula (IV) will also be called repeating unit (a24). In other words, repeating unit (a2) is one or more repeating units selected from the group consisting of repeating units (a22), repeating unit (a23), and repeating unit (a24).

[0081]

[0082] In equation (I), R ３００ This represents a hydrogen atom and a linear or branched alkyl group having 1 to 29 carbon atoms.

[0083]

[0084] In equation (II), u represents 0 or 1. Also, v represents 0 or 1. Also, w represents 0 or 1. Also, R ６１ ~R ７６ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ａ１ and R ｂ１ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R １０２ and R １０３ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Also, R ７５ and R ７６ These elements may be bonded to each other to form a monocycle or polycycle.

[0085]

[0086] In equation (III), t represents an integer from 0 to 10. Also, u represents 0 or 1. Also, v represents 0 or a positive integer. Also, w represents 0 or 1. Also, R ６１~R ７６ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ａ１ and R ｂ１ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R １０４ R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ７５ and R ７６ These elements may be bonded to each other to form a monocycle or polycycle.

[0087]

[0088] In equation (IV), u represents 0 or 1. Also, v represents 0 or 1. Also, w represents 0 or 1. Also, R ６１ ~R ７６ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ａ１ and R ｂ１ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ７５ and R ７６ These elements may be bonded to each other to form a monocycle or polycycle.

[0089]

[0090] In equation (V), u represents 0 or 1. Also, v represents 0 or a positive integer. Also, w represents 0 or 1. Also, R ６１ ~R ７８Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ａ１ and R ｂ１ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ７５ and R ７６ , R ７６ and R ７７ , or R ７７ and R ７８ These elements may be bonded to each other to form a monocycle or polycycle.

[0091] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl groups. Examples of halogenated alkyl groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms. Examples of cycloalkyl groups having 3 to 15 carbon atoms include cyclopentyl and cyclohexyl groups. Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl, naphthyl, tolyl, xylyl, benzyl, and phenylethyl groups.

[0092] From the viewpoint of further improving the balance between release properties and heat resistance, the content of repeating units (a1) in the copolymer (A1) is preferably 10 mol% to 80 mol%, more preferably 30 mol% to 75 mol%, even more preferably 50 mol% to 70 mol%, and even more preferably 53 mol% to 65 mol%, when the total amount of repeating units in the copolymer (A1) is 100 mol%.

[0093] From the viewpoint of further improving the balance between release properties and heat resistance, the content of repeating units (a2) in the copolymer (A1) is preferably 1 mol% to 60 mol%, more preferably 3 mol% to 55 mol%, even more preferably 5 mol% to 45 mol%, and even more preferably 8 mol% to 40 mol%, when the total amount of repeating units in the copolymer (A1) is 100 mol%.

[0094] From the viewpoint of further improving the balance between release properties and heat resistance, the content of repeating units (a3) ​​in the copolymer (A1) is preferably 1 mol% to 50 mol%, more preferably 2 mol% to 45 mol%, even more preferably 3 mol% to 40 mol%, and even more preferably 4 mol% to 38 mol%, when the total amount of repeating units in the copolymer (A1) is 100 mol%.

[0095] (Raw materials for copolymer (A1)) Next, we will explain the raw materials for copolymer (A1).

[0096] Olefins, one of the raw materials for copolymer (A1), are monomers that undergo addition copolymerization to give repeating units (a1) represented by formula (I).

[0097] Examples of monomers that provide the repeating unit (a1) include olefins represented by the following formula (Ia) (hereinafter also referred to as olefin (Ia)).

[0098]

[0099] In equation (Ia), R ３００ This represents a hydrogen atom or a linear or branched alkyl group having 1 to 29 carbon atoms.

[0100] Examples of olefins (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Note that olefins (Ia) may be biomass-derived olefins or chemically recycled olefins. Examples of biomass-derived olefins include biomass-derived ethylene and biomass-derived propylene.

[0101] From the viewpoint of further improving the balance between release properties and heat resistance, the olefin (Ia) preferably includes one or more selected from the group consisting of ethylene and propylene, and more preferably includes ethylene.

[0102] A cyclic non-conjugated diene, one of the raw materials for copolymer (A1), is a monomer that undergoes addition copolymerization to give one or more repeating units (repeating unit (a2)) selected from the group consisting of repeating units (a22) represented by formula (II), repeating units (a23) represented by formula (III), and repeating units (a24) represented by formula (IV).

[0103] Examples of monomers that provide the repeating unit (a22) include cyclic non-conjugated dienes represented by the following formula (IIa) (hereinafter also referred to as cyclic non-conjugated diene (IIa)). Examples of monomers that provide the repeating unit (a23) include cyclic non-conjugated dienes represented by the following formula (IIIa) (hereinafter also referred to as cyclic non-conjugated diene (IIIa)). Examples of monomers that provide the repeating unit (a24) include cyclic non-conjugated dienes represented by the following formula (IVa) (hereinafter also referred to as cyclic non-conjugated diene (IVa)). In other words, examples of monomers that provide the repeating unit (a2) include cyclic non-conjugated dienes (IIa), cyclic non-conjugated dienes (IIIa), and cyclic non-conjugated dienes (IVa).

[0104]

[0105] In equation (IIa), u represents 0 or 1. Also, v represents 0 or 1. Also, w represents 0 or 1. Also, R ６１ ~R ７６ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ａ１ and R ｂ１ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R １０２ and R １０３ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Also, R ７５ and R ７６ These elements may be bonded to each other to form a monocycle or polycycle.

[0106]

[0107] In equation (IIIa), t represents an integer from 0 to 10. Also, u represents 0 or 1. Also, v represents 0 or a positive integer. Also, w represents 0 or 1. Also, R６１ ~R ７６ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ａ１ and R ｂ１ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R １０４ R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ７５ and R ７６ These elements may be bonded to each other to form a monocycle or polycycle.

[0108]

[0109] In equation (IVa), u represents 0 or 1. Also, v represents 0 or 1. Also, w represents 0 or 1. Also, R ６１ ~R ７６ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ａ１ and R ｂ１ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ７５ and R ７６ These elements may be bonded to each other to form a monocycle or polycycle.

[0110] Examples of cyclic non-conjugated dienes (IIa) include 5-ethylidene-2-norbornene, 5-n-propyridene-2-norbornene, 5-isopropylidene-2-norbornene, 5-ethylidene-6-methyl-2-norbornene, and 8-ethylidene-9-methyltetracyclo[4.4.0.1]. ２，５ 1. ７，１０Examples include ]-3-dodecene. Note that the cyclic non-conjugated diene (IIa) may be a cyclic non-conjugated diene derived from biomass or a cyclic non-conjugated diene derived from chemical recycling.

[0111] The cyclic non-conjugated diene (IIa) preferably contains 5-ethylidene-2-norbornene, from the viewpoint of further improving the balance between release properties and heat resistance.

[0112] Examples of cyclic non-conjugated dienes (IIIa) include cyclic non-conjugated dienes represented by the following chemical formula. Note that cyclic non-conjugated dienes (IIIa) may be cyclic non-conjugated dienes derived from biomass or cyclic non-conjugated dienes derived from chemical recycling.

[0113]

[0114]

[0115] From the viewpoint of further improving the balance between release properties and heat resistance, the cyclic non-conjugated diene (IIIa) is preferably 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 ２，５ 1. ７，１０ It comprises one or more species selected from the group consisting of ]-3-dodecene and 5-allyl-2-norbornene.

[0116] Examples of cyclic non-conjugated dienes (IVa) include dicyclopentadiene and pentacyclo[6.5.1.1 ３，６ . 0 ２，７ . 0 ９，１３ Examples include ]-4,10-pentadecadiene. The cyclic non-conjugated diene (IVa) may be a cyclic non-conjugated diene derived from biomass or a cyclic non-conjugated diene derived from chemical recycling.

[0117] From the viewpoint of further improving the balance between release properties and heat resistance, the cyclic non-conjugated diene (IVa) preferably includes dicyclopentadiene.

[0118] The copolymer (A1) may contain double bonds in its side chain portion by including repeating units (a2). Here, the side chain portion refers to the portion of the copolymer (A1) other than the main chain.

[0119] One of the raw materials for copolymer (A1) is a cyclic olefin, which is a monomer that undergoes addition copolymerization to give a repeating unit (a3) ​​represented by formula (V).

[0120] Examples of monomers that provide the repeating unit (a3) ​​include cyclic olefins represented by the following formula (Va) (hereinafter also referred to as cyclic olefins (Va)).

[0121]

[0122] In equation (Va), u represents 0 or 1. Also, v represents 0 or a positive integer. Also, w represents 0 or 1. Also, R ６１ ~R ７８ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ａ１ and R ｂ１ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Also, R ７５ and R ７６ , R ７６ and R ７７ , or R ７７ and R ７８ These elements may be bonded to each other to form a monocycle or polycycle.

[0123] Examples of cyclic olefins (Va) include cyclic olefin monomers described in International Publication No. 2006 / 118261. Note that cyclic olefins (Va) may be biomass-derived or chemically recycled.

[0124] From the viewpoint of further improving the balance between release properties and heat resistance, cyclic olefins (Va) are preferably tetracyclo[4.4.0.1 ２，５ 1. ７，１０ It comprises one or more substances selected from the group consisting of ]-3-dodecene (hereinafter also called tetracyclododecene) and bicyclo[2.2.1]-2-heptene (hereinafter also called norbornene).

[0125] (Other components of copolymer (A1)) Next, repeating units that copolymer (A1) may further contain will be described.

[0126] The copolymer (A1) may contain repeating units other than repeating units (a1), repeating unit (a2), and repeating unit (a3). Examples of repeating units other than repeating units (a1), repeating unit (a2), and repeating unit (a3) ​​include repeating unit (a6) derived from a cyclic olefin represented by formula (VIa) (hereinafter also referred to as cyclic olefin (VIa)), repeating unit (a7) derived from a cyclic olefin represented by formula (VIIa) (hereinafter also referred to as cyclic olefin (VIIa)), and repeating unit (a8) derived from a chain-like polyene represented by formula (VIIIa) (hereinafter also referred to as chain-like polyene (VIIIa)).

[0127]

[0128] In equation (VIa), x and d are integers greater than or equal to 0. Also, y and z are integers between 0 and 2 (inclusive). ８１ ~R ９９ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. Also, R ８９ and R ９０ They may be bonded to each other to form a monoring or polyring. Also, when both y and z are 0, R ９５ and R ９２ or R ９５ and R ９９ These elements may be bonded to each other to form monocyclic or polycyclic aromatic rings.

[0129]

[0130] In equation (VIIa), R １００ and R １０１ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Also, f represents an integer between 1 and 18.

[0131]

[0132] In equation (VIIIa), R ２０１ ~R ２０６ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Furthermore, P represents a direct bond or an alkylene group having 1 to 20 carbon atoms. P may also contain a double or triple bond.

[0133] Examples of cyclic olefins (VIa) include cyclic olefin monomers described in International Publication No. 2006 / 118261.

[0134] Examples of cyclic olefins (VIIa) include cyclic olefin monomers described in International Publication No. 2006 / 118261.

[0135] Examples of linear polyenes (VIIIa) include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, DMDT, 1,3-butadiene, and 1,5-hexadiene.

[0136] From the viewpoint of further improving the balance between release properties and heat resistance, the total content of repeating units (a6), (a7), and (a8) in copolymer (A1) is preferably 10 mol% or less, more preferably 1 mol% or less, even more preferably 0.1 mol% or less, and still more preferably 0 mol%, when the total content of repeating units (a1), (a2), and (a3) ​​in copolymer (A1) is 100 mol%.

[0137] (Method for producing copolymer (A1)) The copolymer (A1) of this embodiment can be produced, for example, according to the method for producing a cyclic olefin copolymer described in paragraphs 0075 to 0219 of International Publication No. 2012 / 046443. The method for producing copolymer (A1) can be, for example, the method described in the examples.

[0138] (Copolymerization Catalyst) In the method for producing the copolymer (A1), for example, a copolymerization catalyst can be used. Examples of copolymerization catalysts include transition metal compounds, organometallic compounds, organoaluminum oxy compounds, and compounds that react with transition metal compounds to form ion pairs. From the viewpoint of increasing the content of repeating units (a2) derived from cyclic non-conjugated dienes in the copolymer (A1), the copolymerization catalyst preferably contains a transition metal compound, and more preferably contains a transition metal compound represented by the following formula (X).

[0139]

[0140] In equation (X), m is an integer from 1 to 4. Also, n is a number that satisfies the valence of Ti. Also, R １ ~R ５ Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Also, R ６ In formula (X), the carbon atom bonded to the phenyl group is a primary, secondary, or tertiary carbon atom; the carbon atom bonded to the phenyl group in formula (X) is a primary, secondary, or tertiary carbon atom; or an aromatic group. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. In formula (X), if m is 2 or more, the R contained in one ligand １ ~R ６ One of the groups and R contained in the other ligands １ ~R６ It may be connected to one of the bases. However, R １ They cannot be combined with each other. Also, R １ Allies, R ２ Allies, R ３ Allies, R ４ Allies, R ５ Fellow, and R ６ The groups may be identical or different from each other. In formula (X), when n is 2 or greater, the multiple groups represented by X may be identical or different from each other. Also, the multiple groups represented by X may bond to each other to form a ring.

[0141] (Properties of Polymer (A)) The number-average molecular weight Mn of Polymer (A), measured by gel permeation chromatography (GPC) in terms of polystyrene, is preferably 1,000 to 100,000, more preferably 2,000 to 80,000, even more preferably 3,000 to 60,000, even more preferably 4,000 to 40,000, even more preferably 5,000 to 30,000, and even more preferably 6,000 to 25,000.

[0142] The number-average molecular weight Mn of polymer (A) is determined by the polymerization catalyst, co-catalyst, and H ２ The polymerization conditions, such as the amount of additive and polymerization temperature, can be controlled. For example, the method described in the examples can be used to measure the number-average molecular weight Mn of polymer (A).

[0143] From the viewpoint of further improving the balance between release properties and heat resistance, the content of polymer (A) in the resin layer (b) is preferably 20% by mass or more and less than 100% by mass, more preferably 30% by mass or more and less than 100% by mass, even more preferably 35% by mass or more and less than 100% by mass, even more preferably 40% by mass or more and less than 100% by mass, and even more preferably 45% by mass or more and less than 100% by mass, when the total amount of solids in the resin layer (b) (total amount of components remaining as solids when cured) is taken as 100% by mass.

[0144] <Reaction Inhibitor (D)> The resin layer (b) preferably further contains a reaction inhibitor (D) from the viewpoint of improving moldability. The reaction inhibitor (D) is, for example, a compound used to control the hydrosilylation reaction by a hydrosilylation agent (C).

[0145] Examples of reaction inhibitors (D) include 1-ethynyl-2-ethyl-1-hexanol, 1-ethynylcyclohexanol, 2-methyl-3-butyne-2-ol, 3,7,11-trimethyl-1-dodecine-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-ethynyl-1-cyclopentanol, 3-methyl-1-dodecine-3-ol, 1,1-diphenyl-2-propyne-1-ol, 3,6-diethyl-1-nonine-3-ol, 3-methyl-1-pentadesine-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,7-dimethyl-3,5-octadiin-2,7-diol, 3-methyl-1-pentin-3-ol, 2,4,7,9-tetramethyl-5-decine-4,7-diol, and 1,4-bis(1 Examples include '-hydroxycyclohexyl)-1,3-butadiine, 1-(1-butynyl)cyclopentanol, 2,5-dimethyl-5-hexen-3-in-2-ol, 5-dimethylamino-2-methyl-3-pentin-2-ol, 3,6-dimethyl-6-hepten-4-in-3-ol, 3-methyl-1-octin-3-ol, 3,4,4-trimethyl-1-pentin-3-ol, 3-isobutyl-5-methyl-1-hexyn-3-ol, 2,5,8-trimethyl-1-nonen-3-in-5-ol, 1-(1-propynyl)cyclohexanol, 3,4-dimethyl-1-pentin-3,4-diol, 2,3,6,7-tetramethyl-4-octin-3,6-diol, and 4-ethyl-1-octin-3-ol.

[0146] The reaction inhibitor (D) preferably comprises one or more selected from the group consisting of 1-ethynyl-2-ethyl-1-hexanol and 1-ethynylcyclohexanol, and more preferably comprises 1-ethynylcyclohexanol, from the viewpoint of further improving the balance between release properties and heat resistance.

[0147] From the viewpoint of further improving the balance between release properties and heat resistance, the content of the reaction inhibitor (D) in the resin layer (b) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 4 parts by mass or less, even more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less, when the content of the polymer (A) in the resin layer (b) is 100 parts by mass. The lower limit of the content of the reaction inhibitor (D) is not particularly limited, but when the content of the polymer (A) in the resin layer (b) is 100 parts by mass, for example it may be 0 parts by mass or more, 0.001 parts by mass or more, or 0.01 parts by mass or more.

[0148] From the viewpoint of further improving the balance between release properties and heat resistance, the content of the reaction inhibitor (D) in the resin layer (b) is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, even more preferably 100 parts by mass or less, even more preferably 80 parts by mass or less, and even more preferably 75 parts by mass or less, when the content of the hydrosilylation agent (C) in the resin layer (b) is 100 parts by mass. The lower limit of the content of the reaction inhibitor (D) is not particularly limited, but when the content of the hydrosilylation agent (C) in the resin layer (b) is 100 parts by mass, for example it may be 0 parts by mass or more, 0.001 parts by mass or more, or 0.01 parts by mass or more.

[0149] <Other Components> The resin layer (b) may contain other components to the extent that they do not hinder the effects of the invention of this embodiment. Examples of other components include resins other than polymer (A), additives, etc. Examples of resins other than polymer (A) include fluororesins; aromatic polymers; homopolymers of cyclic olefins that do not have crosslinking groups; homopolymers of olefins other than cyclic olefins that do not have crosslinking groups; olefin polymers other than polymer (A); epoxy resins, etc. Examples of additives include aromatic polyfunctional monomers, radical polymerization initiators, antioxidants, inorganic fillers, organic fillers, heat stabilizers, weather stabilizers, radiation resistant agents, plasticizers, lubricants, release agents, nucleating agents, friction wear improvers, flame retardants, foaming agents, antistatic agents, colorants, antifogging agents, antiblocking agents, impact resistant agents, surface wetting improvers, hydrochloric acid absorbers, metal deactivators, leveling agents, defoaming agents, etc.

[0150] (Fluorine-based resin) The resin layer (b) may further contain a fluorine-based resin. Examples of fluorine-based resins include fully fluorinated resins and partially fluorinated resins. A fully fluorinated resin means a resin in which all hydrogen atoms in the molecule are replaced with fluorine atoms. A partially fluorinated resin means a resin in which some of the hydrogen atoms in the molecule are replaced with fluorine atoms, or a copolymer of a fluorine resin monomer and a hydrocarbon resin monomer.

[0151] Examples of fully fluorinated resins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).

[0152] Examples of partially fluorinated resins include polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether-chlorotrifluoroethylene copolymer (CPT), ethylene-tetrafluoroethylene-hexafluoropropylene copolymer (EFEP), and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride polymer (THV). Examples of partially fluorinated resins include partially fluorinated hydrocarbon resins, which are hydrocarbon resins that have been partially fluorinated.

[0153] The content of fluororesin in the resin layer (b) is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.5 parts by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, even more preferably 0.01 parts by mass or less, even more preferably 0.005 parts by mass or less, even more preferably 0.001 parts by mass or less, and even more preferably 0 parts by mass, when the content of polymer (A) in the resin layer (b) is 100 parts by mass.

[0154] From the viewpoint of facilitating the processing of the release film after use and improving environmental compatibility, the content of fluorine atoms in the resin layer (b) is preferably 50 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.5 parts by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, even more preferably 0.01 parts by mass or less, even more preferably 0.005 parts by mass or less, even more preferably 0.001 parts by mass or less, and even more preferably 0 parts by mass, when the content of polymer (A) in the resin layer (b) is 100 parts by mass.

[0155] (Aromatic Polymers) The resin layer (b) may further contain aromatic polymers. An aromatic polymer means a polymer having an aromatic ring. Examples of aromatic polymers include phenylene ether resins, oligophenylene ether resins, phenolic resins, melamine resins, aromatic epoxy resins, aromatic polyester resins, aromatic polyimides, aromatic polyamides, aromatic polyamideimides, polydivinylbenzene, oligodivinylbenzene, isotactic polystyrene, syndiotactic polystyrene, atactic polystyrene, aromatic maleimide resins, modified phenylene ether resins, or resins modified from these resins.

[0156] (Olefin polymers other than polymer (A)) The resin layer (b) may further contain olefin polymers other than polymer (A). Examples of olefin polymers other than polymer (A) include polyethylene, polystyrene, polypropylene, cyclic polyolefins, polybutadiene, polymethylpentene, styrene-butadiene-styrene copolymer, styrene-butadiene-butylene-styrene copolymer, styrene-ethylene-butylene-styrene copolymer, ethylene-propylene-ethylidene norbornene copolymer (EPDM), ethylene-propylene-terpolymer (EPT), etc. When the olefin polymer other than polymer (A) is a copolymer, the method of copolymerization is not particularly limited, but examples of copolymerization methods include block copolymerization, alternating copolymerization, random copolymerization, graft copolymerization, etc.

[0157] From the viewpoint of further improving the balance between release properties and heat resistance, the content of olefin polymers other than polymer (A) in the resin layer (b) is preferably 10 parts by mass or more and 1000 parts by mass or less, more preferably 25 parts by mass or more and 400 parts by mass or less, even more preferably 50 parts by mass or more and 200 parts by mass or less, even more preferably 80 parts by mass or more and 125 parts by mass or less, and even more preferably 90 parts by mass or more and 110 parts by mass or less.

[0158] (Aromatic Polyfunctional Monomers) The resin layer (b) may further contain aromatic polyfunctional monomers. An aromatic polyfunctional monomer means a compound having an aromatic ring and two or more crosslinkable groups. Examples of aromatic polyfunctional monomers include aromatic polyenes such as aromatic dienes and aromatic trienes. Examples of aromatic polyenes include divinylbenzene, divinylnaphthalene, divinylanthracene, dipropenylbenzene, diisopropenylbenzene, and 1,2-bis(4-vinylphenyl)ethane.

[0159] From the viewpoint of further improving the balance between release properties and heat resistance, the content of aromatic polyfunctional monomers in the resin layer (b) is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.01 parts by mass or less, even more preferably 0.001 parts by mass or less, and even more preferably 0 parts by mass, when the content of polymer (A) in the resin layer (b) is 100 parts by mass.

[0160] (Radical polymerization initiator) The resin layer (b) may further contain a radical polymerization initiator. Examples of radical polymerization initiators include thermal radical polymerization initiators and photo-radical polymerization initiators. Examples of thermal radical polymerization initiators include dicumyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, 2,2'-azobis(2,4,4-trimethylpentane), benzoyl peroxide, and 2,2'-azobisisobutyronitrile. Examples of photo-radical polymerization initiators include benzoin derivatives (2,2-dimethoxy-2-phenylacetophenone), benzyl ketal, α-hydroxyacetophenone, α-aminoacetophenone (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), and o-acyloxime type photopolymerization initiators.

[0161] (Antioxidant) The resin layer (b) may further contain an antioxidant. Examples of antioxidants (D) include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, thioether-based antioxidants, hindered phenolic antioxidants, and the like.

[0162] The total content of polymer (A) and complex (B) in the resin layer (b) is preferably 20% by mass or more and 100% by mass or less, more preferably 30% by mass or more and 100% by mass or less, even more preferably 35% by mass or more and 100% by mass or less, even more preferably 40% by mass or more and 100% by mass or less, and even more preferably 45% by mass or more and 100% by mass or less, when the total amount of resin layer (b) (total amount of components remaining as solid matter when cured) is taken as 100% by mass.

[0163] The resin layer (b) may be in an uncured or semi-cured state.

[0164] <Method for forming resin layer (b)> Examples of methods for forming resin layer (b) include the following steps 1 to 3. More specifically, the method for forming resin layer (b) can be the method described in the examples.

[0165] (Step 1: Preparation of resin composition) A resin composition is prepared by mixing a polymer (A) and, if necessary, other components such as a complex (B), a hydrosilylater (C), and a reaction inhibitor (D). As a mixing method, a solution blending method, in which the components are dissolved or dispersed in a solvent, can be employed. In this case, examples of solvents include saturated hydrocarbons and aromatic hydrocarbons. Examples of saturated hydrocarbons include heptane, hexane, decane, and cyclohexane. Examples of aromatic hydrocarbons include toluene, benzene, and xylene.

[0166] (Step 2: Preparation of varnish) The varnish is prepared by mixing the resin composition and solvent described above. Apparatus for preparing the varnish can be, for example, a batch-type apparatus capable of stirring and mixing, or a continuous-type apparatus capable of stirring and mixing. The temperature when preparing the varnish can be arbitrarily selected within the range from room temperature to the boiling point of the solvent. Alternatively, the varnish may be prepared by using the reaction solution obtained when polymer (A) is obtained as is.

[0167] The solvent included in the varnish is not particularly limited as long as it does not impair the solubility or affinity of the polymer (A), complex (B), hydrosilylater (C), and reaction inhibitor (D). Examples of solvents used in the varnish include linear saturated hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, ketones, cellosolves, esters, halogenated hydrocarbons, and ethers.

[0168] Examples of linear saturated hydrocarbons include heptane, hexane, octane, and decane. Examples of alicyclic hydrocarbons include cyclohexane, methylcyclohexane, and decahydronaphthalene. Examples of aromatic hydrocarbons include toluene, benzene, xylene, mesitylene, and pseudocumene. Examples of alcohols include methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol. Examples of ketones include acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone. Examples of cellosolves include methyl cellosolve and ethyl cellosolve. Examples of esters include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate. Examples of halogenated hydrocarbons include trichloroethylene, dichloroethylene, and chlorobenzene. Examples of ethers include tetrahydrofuran and diethyl ether.

[0169] The solvent used in the varnish preferably comprises one or more selected from the group consisting of heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, pseudocumene, and cyclohexanone, from the viewpoint of improving the performance balance between the solubility of the resin composition and the ease of availability, more preferably comprises one or more selected from the group consisting of toluene, cyclohexane, and cyclohexanone, and even more preferably comprises toluene.

[0170] From the viewpoint of improving the balance between the handling and coating properties of the varnish, the amount of solvent added to the resin composition is preferably 50 parts by mass or more and 2000 parts by mass or less, more preferably 100 parts by mass or more and 1900 parts by mass or less, even more preferably 200 parts by mass or more and 1800 parts by mass or less, even more preferably 300 parts by mass or more and 1700 parts by mass or less, and even more preferably 400 parts by mass or more and 1600 parts by mass or less.

[0171] (Step 3: Formation of resin layer (b)) Methods for forming the resin layer (b) include, for example, applying the above-mentioned varnish to a support substrate, drying it, and then crosslinking the resin composition to form the resin layer (b). Examples of support substrates include thermoplastic resin films such as PET film and polyimide film. Methods for applying the varnish to the support substrate include, for example, application using a coater. Examples of coaters include spin coaters, spray coaters, bar coaters, roll coaters, gravure coaters, small-diameter gravure coaters, reverse gravure coaters, and bank coaters. Another method for forming the resin layer (b) is to form the resin layer (b) by melting and then crosslinking the resin composition to create a cured product.

[0172] The resin layer (b) can be produced by crosslinking the polymer (A) in the resin composition. The cured product can be produced, for example, by crosslinking the resin composition under conditions of a crosslinking temperature of 150°C or higher. The crosslinking of polymer (A) may be carried out in air or in an inert atmosphere. Examples of an inert atmosphere include nitrogen and argon. Furthermore, the crosslinking of polymer (A) may be carried out under normal pressure or under reduced pressure.

[0173] The crosslinking temperature is preferably 150°C or higher, more preferably 160°C or higher, and even more preferably 170°C or higher, from the viewpoint of improving the heat resistance of the cured product. Furthermore, the crosslinking temperature is preferably 350°C or lower, more preferably 340°C or lower, even more preferably 330°C or lower, even more preferably 320°C or lower, even more preferably 310°C or lower, and even more preferably 300°C or lower, from the viewpoint of reducing excessive oxidation of the polymer (A) and the cured product.

[0174] The crosslinking reaction may be carried out with the resin composition in a molten state, or with the resin composition dissolved or dispersed in a solvent in a solution state. Alternatively, the crosslinking reaction may be carried out with the resin composition in the form of a film, sheet, or the like. The formation of the film, sheet, etc., may be carried out, for example, by volatilizing the solvent or dispersion medium from the solution state.

[0175] <Intermediate layer (c)> The release film may further include an intermediate layer (c) between the base layer (a) and the resin layer (b). This improves the mechanical properties of the release film and enhances its transportability and handling. Examples of resins that make up the intermediate layer (c) include thermosetting resins, photocurable resins, thermoplastic resins, etc. The intermediate layer (c) may be a single layer or a layer consisting of two or more layers.

[0176] <Characteristics of the release film> The characteristics of the release film of this embodiment will be described below.

[0177] Regarding the release film of this embodiment, the peel strength P is determined by the following (Method 1). ０ Explain.

[0178] Peel strength P ０ From the viewpoint of further improving the performance balance between release properties and heat resistance, the peel strength P is preferably 5.0 N / 19 mm or less, more preferably 4.5 N / 19 mm or less, even more preferably 4.0 N / 19 mm or less, even more preferably 3.5 N / 19 mm or less, even more preferably 3.0 N / 19 mm or less, even more preferably 2.5 N / 19 mm or less, and even more preferably 2.0 N / 19 mm or less. ０The lower limit is not particularly restricted, but it may be, for example, 0 N / 19 mm or higher, 0.01 N / 19 mm or higher, or 0.1 N / 19 mm or higher.

[0179] (Method 1) A 30 mm x 130 mm test specimen is prepared from the release film. Next, an adhesive tape with a thickness of 25 μm and a width of 19 mm is attached to the surface of the test specimen on the resin layer (b) side. Then, using a peel strength measuring device, the 90° peel strength is measured by the tape peel method under the conditions of 25°C, 80% RH or less, load cell 5 kgf, crosshead speed 300 mm / min, and chart speed 30 mm / min.

[0180] Peel strength P ０ This can be adjusted, for example, by adjusting the composition of the release film, the manufacturing conditions of the release film, the type of polymer (A), the type of complex (B), etc. Note that the peel strength P ０ For example, the measurement method described in the examples can be employed.

[0181] Regarding the release film of this embodiment, the peel strength P is determined by the following (Method 2). １ Explain.

[0182] Peel strength P １ From the viewpoint of further improving the performance balance between release properties and heat resistance, the peel strength P is preferably 5.0 N / 19 mm or less, more preferably 4.5 N / 19 mm or less, even more preferably 4.0 N / 19 mm or less, even more preferably 3.5 N / 19 mm or less, even more preferably 3.0 N / 19 mm or less, even more preferably 2.5 N / 19 mm or less, and even more preferably 2.0 N / 19 mm or less. １ The lower limit is not particularly restricted, but it may be, for example, 0 N / 19 mm or higher, 0.01 N / 19 mm or higher, or 0.1 N / 19 mm or higher.

[0183] (Method 2) A 30 mm x 130 mm test specimen is prepared from the release film. Next, a structure is prepared by sandwiching the test specimen between two 0.3 mm thick SUS plates. Next, the structure is heated at 350°C for 1 minute using a small test press. Next, the structure is cooled to 30°C by leaving it in the small test press set to 30°C for 3 minutes. Next, the test specimen is removed from the structure. Next, an adhesive tape with a thickness of 25 μm and a width of 19 mm is attached to the surface of the test specimen on the resin layer (b) side. Next, the 90° peel strength is measured using the tape peel method with a peel strength measuring device under the conditions of 25°C, 80% RH or less, load cell 5 kgf, crosshead speed 300 mm / min, and chart speed 30 mm / min.

[0184] Peel strength P １ This can be adjusted, for example, by adjusting the composition of the release film, the manufacturing conditions of the release film, the type of polymer (A), the type of complex (B), etc. Note that the peel strength P １ For example, the measurement method described in the examples can be employed.

[0185] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., that do not impair the effects of the present invention are included in the present invention.

[0186] This embodiment will be described in detail below with reference to examples and other relevant information. However, this embodiment is not limited in any way to the descriptions of these examples.

[0187] First, let's explain the materials used in each example. • Polymer (A) (Copolymer (A1)) Copolymer 1: Synthesis Example 1 described later (Content of repeating unit (a1): 62 mol%, Content of repeating unit (a2): 27 mol%, Content of repeating unit (a3): 11 mol%, Number average molecular weight Mn: 22,300) Copolymer 2: Synthesis Example 2 described later (Content of repeating unit (a1): 62 mol%, Content of repeating unit (a2): 27 mol%, Content of repeating unit (a3): 11 mol%, Number average molecular weight Mn: 11,300) Copolymer 3: Synthesis Example 3 described later (Content of repeating unit (a1): 58 mol%, Content of repeating unit (a2): 36 mol%, Content of repeating unit (a3): 6 mol%, Number average molecular weight Mn: 11,500) Copolymer 4: Synthesis example 4 described below (content of repeating unit (a1) is 56 mol%, content of repeating unit (a2) is 10 mol%, content of repeating unit (a3) ​​is 34 mol%, number average molecular weight Mn is 6,620) Complex (B) Platinum complex 1: Platinum catalyst (1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complex, CAS number: 68478-92-2, 5% by mass toluene solution) Platinum complex 2: Platinum catalyst (Platinum(0)-2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex, CAS number: 68585-32-0, 50% by mass toluene solution) Platinum complex 3: Platinum catalyst (hexachloroplatinic acid hexahydrate, CAS number: 18497-13-7, 5% by mass cyclohexanone solution) ・Hydrosilylation agent (C) Hydrosilylation agent 1: Hydrosilyl group-containing compound (trimethylsiloxy-terminated methylhydrogen siloxane, CAS number: 63148-57-2) (hereinafter also referred to as HS agent 1.) Hydrosilylation agent 2: Hydrosilyl group-containing compound (1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, CAS number: 17875-55-7) (hereinafter also referred to as HS agent 2.) Hydrosilylation agent 3: Hydrosilyl group-containing compound (phenyltris(dimethylsiloxy)silane, CAS number: 18027-45-7) (hereinafter also referred to as HS agent 3.) ・Reaction inhibitor (D) Reaction inhibitor 1: 1-ethynylcyclohexanol (manufactured by Nisshin Chemical Industry Co., Ltd.) (hereinafter also referred to as inhibitor 1).) ・Radical initiator: Dicumyl peroxide (product name: Perkmyl D, manufactured by NOF Corporation) (hereinafter also referred to as initiator 1). ・Olefin polymers other than polymer (A) Olefin polymer 1: Styrene-butadiene-styrene copolymer (product name: Toughprene 126S, manufactured by Asahi Kasei Corporation) (hereinafter also referred to as copolymer 5). Olefin polymer 2: Partially hydrogenated styrene-butadiene-butylene-styrene copolymer (Toughtec P1500, manufactured by Asahi Kasei Corporation) (hereinafter also referred to as copolymer 6). Olefin polymer 3: Thermoplastic cyclic olefin copolymer (APL6509T, manufactured by Mitsui Chemicals, Inc.) (hereinafter also referred to as copolymer 7).

[0188] The following materials were used in Comparative Examples 1 and 2, described later: • PTFE film (Product name: TOMBO9001 PTFE sheet, manufactured by Nichias Corporation) • PI film (Product name: UPILEX 25S, manufactured by UBE Corporation)

[0189] Next, we will explain the methods for preparing copolymers 1 to 4 and the methods for measuring their physical properties (content of each repeating unit and number-average molecular weight Mn). First, we will explain the methods for preparing copolymers 1 to 4. The following raw materials were used for the synthesis of copolymers 1 to 4.

[0190] • Transition metal compound (1): Synthesized by the method described in Synthesis Example 1 of Japanese Patent Publication No. 2004-331965.

[0191] Modified methylaluminoxane (product name: MMAO-3A, ​​manufactured by Tosoh Finechem Co., Ltd.) (hereinafter also referred to as MMAO) Ethylene (manufactured by Mitsui Chemicals, Inc.) 5-vinyl-2-norbornene (manufactured by Tokyo Chemical Industries, Ltd.) (hereinafter also referred to as VNB) Tetracyclo[4.4.0.1 ２，５ 1. ７，１０]-3-Dodecene (manufactured by Mitsui Chemicals, Inc.) (hereinafter also referred to as TD) 2-Norbornene (manufactured by Tokyo Chemical Industries, Ltd.) (hereinafter also referred to as NB) Toluene (dehydrated toluene, manufactured by Kanto Chemical Co., Ltd.) Acetone (manufactured by Kanto Chemical Co., Ltd.) Methanol (manufactured by Kanto Chemical Co., Ltd.) Cyclohexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Cyclohexanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0192] Next, copolymers 1 to 4 were prepared using the following methods.

[0193] [Synthesis Example 1: Copolymer 1] In a 1000 mL stainless steel autoclave with a volume of 1000 mL that had been thoroughly purged with nitrogen, 455 mL of toluene, 29 mL of VNB, 16 mL of TD, a hexane solution of MMAO (0.8 mmol in terms of aluminum atoms), and 446 mL of hydrogen were added. Then, ethylene was added to the stainless steel autoclave until the total pressure reached 0.6 MPa. Next, a toluene solution containing 0.028 mmol of transition metal compound (1) was added to the stainless steel autoclave, and polymerization was carried out at 35°C for 50 minutes. After that, polymerization was terminated by adding 1 mL of methanol. After polymerization, deionized water was added to the obtained solution and stirred for 1 hour, and then the organic layer was filtered through filter paper. The filtered organic layer was added to a mixed solvent of acetone and methanol to precipitate the polymer. Next, the mixed solvent on which the polymer had precipitated was stirred and filtered through filter paper. Then, the obtained polymer was dried under reduced pressure at 80°C for 10 hours to obtain copolymer 1 consisting of ethylene / VNB / TD.

[0194] [Synthesis Example 2: Copolymer 2] By adjusting the amount of each raw material and the reaction conditions compared to the synthesis procedure for copolymer 1, copolymer 2 consisting of ethylene / VNB / TD was obtained.

[0195] [Synthesis Example 3: Copolymer 3] By adjusting the amount of each raw material and the reaction conditions compared to the synthesis procedure for copolymer 1, copolymer 3 consisting of ethylene / VNB / NB was obtained.

[0196] [Synthesis Example 4: Copolymer 4] By adjusting the amount of each raw material and the reaction conditions compared to the synthesis procedure for copolymer 1, copolymer 4 consisting of ethylene / VNB / TD was obtained.

[0197] Next, the methods for measuring the physical properties of copolymers 1 to 4 will be described. The content of repeating units (a1), (a2), and (a3) ​​in copolymers 1 to 4 was measured according to the following (Method for measuring the content of each repeating unit). In addition, the number-average molecular weight Mn of copolymers 1 to 4 was measured according to the following (Method for measuring the number-average molecular weight Mn).

[0198] (Method for measuring the content of each repeating unit) Using a nuclear magnetic resonance spectrometer (product name: EXcalibur 270, manufactured by JEOL Ltd.), copolymers 1 to 4 were measured as follows: １ The 1H-NMR spectra were measured for each sample. １ 1H-NMR measurements were performed under conditions of 16 to 64 cumulative cycles at room temperature of 25°C. １ From the 1H-NMR spectrum, the content of repeating units (a1), (a2), and (a3) ​​was calculated based on the intensity of the peaks derived from hydrogen directly bonded to the double bond carbon and the peaks derived from other hydrogen atoms.

[0199] (Method for measuring number-average molecular weight Mn) The number-average molecular weight Mn of copolymers 1 to 4 dissolved in o-dichlorobenzene-d4 was measured using a gel permeation chromatograph (product name: HLC-8321 GPC / HT type, manufactured by Tosoh Corporation). GPC measurements were performed under the following conditions: Molecular weight calibration: Monodisperse polystyrene standard (manufactured by Tosoh Corporation) Data processing software: Empower3 (manufactured by Waters Inc.) Detector: Bryce type double-pass, dual-flow RI detector (built-in type) (manufactured by Tosoh Corporation) Column: TSKgel GMH6-HT (manufactured by Tosoh Corporation) and TSKgel GMH6-HTL (manufactured by Tosoh Corporation) connected in series in that order Column temperature: 140°C Sample concentration: 0.1% (w / v) Injection volume: 400 μL Sampling interval: 0.5 seconds Flow rate: 1.0 ml / min

[0200] Next, the preparation methods for each example and each comparative example will be described.

[0201] [Example 1] (Varnish Preparation) Copolymer 1 and other materials were weighed according to the formulation composition shown in Table 1. Then, each weighed material was stirred in the solvent until it was completely dissolved to obtain varnish 1. Note that the unit of the formulation ratio of each raw material in Table 1 is parts by mass. Also, the mass of complex (B) is the mass of the entire solution.

[0202] (Preparation of release film) A coated film 1 was prepared by coating a polyimide film (product name: UPILEX 25S, manufactured by UBE Corporation, thickness 25 μm) with varnish 1 using an automatic film coating machine (product name: PI-1210, manufactured by Tester Sangyo Co., Ltd.). The varnish 1 was applied under the following conditions: applicator gap of 150 μm, coating speed of 10 mm / second, and room temperature air (25°C, 80% RH or less). Next, a dried film 1 was obtained by drying the coated film 1 using a dryer (product name: STPH-102M, manufactured by ESPEC Corporation). The drying of the coated film 1 was carried out under the conditions of 150°C for 4 minutes and an airflow with an oxygen concentration of 17 ± 3%. Next, a cured film 1 (total thickness 35 ± 5 μm) was obtained by heating and curing the dried film 1 using a dryer (product name: STPH-102M, manufactured by ESPEC Corporation). The drying film 1 was heated at 260°C for 10 minutes under an airflow with an oxygen concentration of 17±3%. The cured film 1 produced in this manner was designated as the release film 1. In the release film 1, the polyimide film corresponds to the base layer (a). In the release film 1, the layer obtained by drying and curing the varnish 1 coated on the polyimide film corresponds to the resin layer (b).

[0203] [Examples 2-16] Release films 2-16 were prepared in the same manner as in Example 1, except that the material composition was changed to the composition shown in Table 1 corresponding to each example.

[0204] [Comparative Examples 1-2] Comparative Example 1 used a PTFE film. Comparative Example 2 used a PI film.

[0205] The properties of the films were measured or evaluated according to the method described below. The results are shown in Table 1. In the following, the release films 1 to 16 of Examples 1 to 16, the PTFE film of Comparative Example 1, and the PI film of Comparative Example 2 may be collectively referred to as the "film of each example."

[0206] [Peel strength P] ０ [Measurement] First, a 30 mm x 130 mm test piece 1 was prepared from the film of each example. Next, an adhesive tape with a thickness of 25 μm and a width of 19 mm (product name: Polyester Adhesive Tape No. 31B, manufactured by Nitto Denko Corporation) was attached to the surface of the test piece 1 on the resin layer (b) side. Then, the 90° peel strength was measured using the tape peel method with a peel strength measuring device (product name: Strograph E-S, manufactured by Toyo Seiki Seisakusho Co., Ltd.). The 90° peel strength was measured under the following conditions: 25°C, 80% RH or less, load cell 5 kgf, crosshead speed 300 mm / min, and chart speed 30 mm / min.

[0207] [Peel strength P] １ [Measurement] A 30 mm x 130 mm test piece 2 was prepared from the film of each example. Next, a structure 2 was prepared by sandwiching the test piece 2 between two SUS plates (0.3 mm thick, made of SUS304). Using a small test press (product name: Mini Test Press MP-WCH, manufactured by Toyo Seiki Seisakusho Co., Ltd.), the structure 2 was heated at 350°C for 1 minute at 1 MPa. Next, the structure 2 was cooled to 30°C by leaving it sandwiched in the small test press set to 30°C for 3 minutes. Next, the test piece 2 was removed from the structure 2. Next, an adhesive tape with a thickness of 25 μm and a width of 19 mm (product name: Polyester Adhesive Tape No. 31B, manufactured by Nitto Denko Corporation) was attached to the surface of the test piece 2 on the resin layer (b) side. Next, the 90° peel strength was measured using the tape peel method with a peel strength measuring device (product name: Strograph E-S, manufactured by Toyo Seiki Seisakusho Co., Ltd.). The 90° peel strength was measured under the following conditions: 25°C, 80% RH or less, load cell 5 kgf, crosshead speed 300 mm / min, and chart speed 30 mm / min.

[0208] [Heat Resistance Evaluation] A 50 mm x 50 mm test piece 3 was prepared from the film of each example. Next, a structure 3 was prepared by sandwiching the test piece 3 between two SUS plates (0.3 mm thick, made of SUS304). Using a small test press (product name: Mini Test Press MP-WCH, manufactured by Toyo Seiki Seisakusho Co., Ltd.), the structure 3 was heated at 350°C for 1 minute under the conditions of 1 MPa. Next, the structure 3 was cooled to 30°C by leaving it sandwiched in the small test press set to 30°C for 3 minutes. Then, the test piece 3 was removed from the structure 3. In the removed test piece 3, if no deformation of 5 mm or more in dimensions was observed on any of the four sides of the test piece 3 before and after heat pressing, it was evaluated as A, and if deformation was observed, it was evaluated as B.

[0209] [Evaluation of Adhesion to Substrate] A 50 mm x 50 mm test piece 4 was prepared from the film of each example. Next, a structure 4 was prepared by sandwiching the test piece 4 between two SUS plates (0.3 mm thick, made of SUS304). Using a small test press (product name: Mini Test Press MP-WCH, manufactured by Toyo Seiki Seisakusho Co., Ltd.), the structure 4 was heated at 350°C for 1 minute at 1 MPa. Next, the structure 4 was cooled to 30°C by leaving it sandwiched in the small test press set to 30°C for 3 minutes. Then, the test piece 4 was removed from the structure 4. When the test piece 4 was removed from the structure 4, it was visually confirmed whether the surface of the varnished side of the test piece 4 could be easily peeled off from the SUS plate. If the surface of test piece 4 on the side coated with varnish was not adhered to the SUS plate, it was evaluated as A. If the surface of test piece 4 on the side coated with varnish was partially or completely adhered to the SUS plate, it was evaluated as B.

[0210]

[0211] This application claims priority based on Japanese Patent Application No. 2024-199501, filed on 15 November 2024, and incorporates all of its disclosures herein.

[0212] 10 Base layer (a) 20 Resin layer (b) 30 Intermediate layer (c) 200 Release film

Claims

1. A heat-resistant release film comprising a base layer (a) and a resin layer (b) containing an olefin polymer (A) having crosslinkable groups.

2. The heat-resistant release film according to claim 1, wherein the base layer (a) comprises one or more selected from the group consisting of polyimide resin, modified polyimide resin, polyamideimide resin, polyetheretherketone resin, polyaryletherketone resin, silicone resin, and modified silicone resin.

3. The heat-resistant release film according to claim 1 or 2, wherein the resin layer (b) further comprises a complex (B), and the complex (B) comprises a metal atom and a ligand.

4. The heat-resistant release film according to claim 3, wherein the ligand has a total of two or more ligands selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds, and has an organosiloxane structure.

5. The heat-resistant release film according to claim 4, wherein the ligand contains a ligand represented by the following formula (L1). [In the formula (L1), n represents an integer of 0 or more, and R １１ to R １６ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms, and R ２１ to R ２４ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or an organosiloxane group having 1 to 20 silicon atoms, X each independently represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R １１ and R １２ , R １１ and R １３ , R １２ and R １３ , R １４ and R １５ , R １４ and R １６ , R １５ and R １６ , R ２１ and R ２２ , R ２１ and R ２３ , R ２１ and R ２４ , R ２２ and R ２３ , R ２２ and R ２４ , or R ２３ and R ２４ may be bonded to each other to form a monocyclic or polycyclic ring. ] 6. The heat-resistant release film according to claim 3, wherein the content of the complex (B) in the resin layer (b) is 0.0001 parts by mass or more and 5 parts by mass or less, when the content of the olefin polymer (A) in the resin layer (b) is 100 parts by mass.

7. The heat-resistant release film according to claim 1 or 2, wherein the resin layer (b) further comprises a hydrosilylation agent (C) having a hydrosilyl group and a siloxane structure.

8. The heat-resistant release film according to claim 7, wherein the hydrosilylated agent (C) comprises a compound represented by the following formula (H1). [In the above formula (H1), m １ represents a positive integer, and m ２ R represents a non-negative integer, ３１ ~R ３９ Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or an organosiloxane group having 1 to 20 silicon atoms.

9. The heat-resistant release film according to claim 7, wherein the content of the hydrosilylated agent (C) in the resin layer (b) is 0.01 parts by mass or more and 10 parts by mass or less, when the content of the olefin polymer (A) in the resin layer (b) is 100 parts by mass.

10. The heat-resistant release film according to claim 1 or 2, wherein the content of fluorine atoms in the resin layer (b) is 50 parts by mass or less, when the content of the olefin polymer (A) in the resin layer (b) is 100 parts by mass.

11. The heat-resistant release film according to claim 1 or 2, wherein the olefin polymer (A) comprises a cyclic olefin copolymer (A1) having a crosslinkable group.

12. The heat-resistant release film according to claim 11, wherein the cyclic olefin copolymer (A1) comprises a repeating unit (a1) represented by the following formula (I), one or more repeating units (a2) selected from the group consisting of a repeating unit represented by the following formula (II), a repeating unit represented by the following formula (III), and a repeating unit represented by the following formula (IV), and a repeating unit (a3) ​​represented by the following formula (V). [In the above formula (I), R ３００ This represents a hydrogen atom or a linear or branched alkyl group having 1 to 29 carbon atoms. [In formula (II) above, u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, R ６１ ~R ７６ , R ａ１ , and R ｂ１ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R １０２ and R １０３ Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ７５ and R ７６ These may be bonded to each other to form a monocycle or polycycle. [In formula (III) above, t represents an integer from 0 to 10, u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, R ６１ ~R ７６ , R ａ１ , and R ｂ１ Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R １０４ R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ７５ and R ７６ These may be bonded to each other to form a monocycle or polycycle. [In the above formula (IV), u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, and R ６１ ~R ７６ 、R ａ１ 、and R ｂ１ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring. ] [In the above formula (V), u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, and R ６１ ~R ７８ 、R ａ１ 、and R ｂ１ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ７５ and R ７６ 、R ７６ and R ７７ 、or R ７７ and R ７８ may be bonded to each other to form a monocyclic or polycyclic ring. ] 13. The heat-resistant release film according to claim 12, wherein the olefin constituting the repeating unit (a1) contains ethylene.

14. The cyclic non-conjugated diene constituting the repeating unit (a2) is 5-vinyl-2-norbornene, 8-vinyl-9-methyltetracyclo[4.4.0.1 ２，５ 1. ７，１０ A heat-resistant release film according to claim 12, comprising one or more selected from the group consisting of ]-3-dodecene and 5-allyl-2-norbornene.

15. The cyclic olefin constituting the repeating unit (a3) ​​is tetracyclo[4.4.0.1 ２，５ 1. ７，１０ The heat-resistant release film according to claim 12, comprising one or more selected from the group consisting of ]-3-dodecene and bicyclo[2.2.1]-2-heptene.

16. The heat-resistant release film according to claim 1 or 2, wherein the resin layer (b) further comprises a reaction inhibitor (D).

17. The heat-resistant release film according to claim 16, wherein the content of the reaction inhibitor (D) in the resin layer (b) is 10 parts by mass or less, when the content of the olefin polymer (A) in the resin layer (b) is 100 parts by mass.

18. The heat-resistant release film according to claim 1 or 2, wherein the resin layer (b) is in an uncured or semi-cured state.

19. The heat-resistant release film according to claim 1 or 2, wherein the thickness of the base material layer (a) is 1 μm or more and 100 μm or less.

20. The heat-resistant release film according to claim 1 or 2, wherein the thickness of the resin layer (b) is 0.1 μm or more and 50 μm or less.

21. Peel strength P by the following (Method 1) ０ A heat-resistant release film according to claim 1 or 2, wherein the strength is 5.0 N / 19 mm or less. (Method 1) A 30 mm x 130 mm test piece is prepared from the heat-resistant release film. Then, an adhesive tape with a thickness of 25 μm and a width of 19 mm is attached to the surface of the test piece on the resin layer (b) side. Then, the 90° peel strength is measured using a peel strength measuring device by the tape peel method under the conditions of 25°C, 80% RH or less, load cell 5 kgf, crosshead speed 300 mm / min, and chart speed 30 mm / min.

22. Peel strength P by the following method (Method 2) １ A heat-resistant release film according to claim 1 or 2, wherein the strength is 5.0 N / 19 mm or less. (Method 2) A 30 mm x 130 mm test piece is prepared from the heat-resistant release film. A structure is then prepared by sandwiching the test piece between two SUS plates with a thickness of 0.3 mm. The structure is then heated at 350°C for 1 minute using a small test press. The structure is then cooled to 30°C by leaving it sandwiched in the small test press set to 30°C for 3 minutes. The test piece is then removed from the structure. A 25 μm thick, 19 mm wide adhesive tape is then attached to the surface of the test piece on the resin layer (b) side. The 90° peel strength is then measured using a peel strength measuring device by the tape peel method at 25°C, 80% RH or less, load cell 5 kgf, crosshead speed 300 mm / min, and chart speed 30 mm / min.

23. The heat-resistant release film according to claim 1 or 2, which is a heat-resistant release film used in semiconductor manufacturing processes.

Images