Resin composition, cured product, film, laminated film, and release film

Abstract

A resin composition comprising: an olefin-based polymer (A) having a crosslinkable group; and a complex (B) comprising a metal atom and a ligand, wherein the content of the complex (B) is from 0.0001 to 5 parts by mass relative to 100 parts by mass of the olefin-based polymer (A).

Description

Resin compositions, cured products, films, laminated films, and release films

[0001] The present invention relates to resin compositions, cured products, films, laminated films, and release films.

[0002] For example, release films are used in semiconductor manufacturing processes, mold release processes used when forming structural components, high-bandwidth memory manufacturing processes, mold release processes for multilayer semiconductor encapsulants, and mold release processes within office automation equipment. 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 the conventional release film, it has been difficult to achieve both release properties and heat resistance. The present invention provides a resin composition capable of obtaining a film with an improved balance between release properties and heat resistance.

[0007] According to the present invention, there are provided a resin composition, a cured product, a film, a laminated film, and a release film as shown below. [1] A resin composition comprising an olefin polymer (A) having a crosslinkable group and a complex (B), wherein the complex (B) contains a metal atom and a ligand, and the content of the complex (B) is 0.0001 parts by mass or more and 5 parts by mass or less when the content of the olefin polymer (A) is 100 parts by mass. [2] The resin composition according to [1], wherein the ligand has a total of two or more of one or more selected from the group consisting of a carbon-carbon double bond and a carbon-carbon triple bond and has an organosiloxane structure. [3] The resin composition according to [1] or [2], wherein the ligand contains a ligand represented by the following formula (L1). (In the above formula (L1), n represents an integer of 0 or more, and R １１ to 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, and R ２１ to 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 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 R２２ , 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 These may be bonded to each other to form a monocycle or polycycle. ] [4] The resin composition according to any one of [1] to [3], further comprising a hydrosilylation agent (C) having a hydrosilyl group and a siloxane structure. [5] The resin composition according to [4], 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 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. [6] The resin composition according to [4] or [5], wherein the content of the hydrosilylation agent (C) is 0.01 parts by mass or more and 10 parts by mass or less when the content of the olefin polymer (A) is 100 parts by mass. [7] The resin composition according to any one of [1] to [6], wherein the content of the fluorine atom is 50 parts by mass or less when the content of the olefin polymer (A) is 100 parts by mass. [8] The resin composition according to any one of [1] to [7], wherein the olefin polymer (A) comprises a cyclic olefin copolymer (A1) having a crosslinkable group. [9] The resin composition according to [8], 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 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 ７５and 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 ７８ These may be bonded to each other to form a monocycle or polycycle. ]

[10] The resin composition according to [9], wherein the olefin constituting the repeating unit (a1) contains ethylene.

[11] 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 The resin composition according to [9] or

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

[12] The cyclic olefin constituting the repeating unit (a3) ​​is tetracyclo[4.4.0.1 ２，５ 1. ７，１０ A resin composition according to any one of [9] to

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

[13] A resin composition according to any one of [1] to

[12] , further comprising a reaction inhibitor (D).

[14] A resin composition according to

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

[15] A resin composition according to any one of [1] to

[14] , which is in an uncured or semi-cured state.

[16] Peel strength P according to the following (Method 1) ０A resin composition according to any one of [1] to

[15] above, wherein the strength is 5.0 N / 19 mm or less. (Method 1) A coated film is prepared by coating a polyimide film with a thickness of 25 μm with a varnish containing the resin composition. The coated film is then dried at 150°C for 4 minutes under an airflow with an oxygen concentration of 17 ± 3%, and then heated at 260°C for 10 minutes under an airflow with an oxygen concentration of 17 ± 3% to prepare a cured film with a thickness of 35 ± 5 μm. A test piece measuring 30 mm × 130 mm is then prepared from the cured film. An adhesive tape measuring 25 μm thick and 19 mm wide is then attached to the surface of the test piece on the side coated with the varnish. The 90° peel strength is then 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.

[17] Peel strength P by the method described below (Method 2) １A resin composition according to any one of [1] to

[16] , wherein the ratio is 5.0 N / 19 mm or less. (Method 2) A coated film is prepared by coating a polyimide film with a thickness of 25 μm with a varnish containing the resin composition. The coated film is then dried at 150°C for 4 minutes under an airflow with an oxygen concentration of 17 ± 3%, and then heated at 260°C for 10 minutes under an airflow with an oxygen concentration of 17 ± 3% to prepare a cured film with a thickness of 35 ± 5 μm. A test piece measuring 30 mm × 130 mm is then prepared from the cured 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. Next, an adhesive tape 25 μm thick and 19 mm wide is attached to the surface of the test piece coated with the varnish, and 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.

[18] A cured product of the resin composition according to any one of [1] to

[17] .

[19] A film comprising the resin composition according to any one of [1] to

[17] or a cured product of the resin composition.

[20] A laminated film comprising a base layer (a) and a resin layer (b) comprising the film according to

[19] .

[21] The laminated film according to

[20] , 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.

[22] The laminated film according to

[20] or

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

[23] The laminated film according to any one of

[20] to

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

[24] A release film comprising the film described in

[19] or the laminated film described in any of

[20] to

[23] .

[0008] According to the present invention, it is possible to provide a resin composition that can produce a film with an improved balance of release properties and heat resistance.

[0009] This is a schematic cross-sectional view showing an example of the structure of the laminated film of this embodiment. This is a schematic cross-sectional view showing an example of the structure of the release film of this embodiment. This is a schematic cross-sectional view showing an example of the structure of the release film of 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] [Resin Composition] The resin composition of this embodiment contains an olefin polymer (A) having a crosslinkable group. The resin composition of this embodiment contains a complex (B). In the resin composition of this embodiment, the complex (B) contains a metal atom and a ligand. In the resin composition of this embodiment, the content of the complex (B) is 0.0001 parts by mass or more and 5 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass. By having the above configuration, the resin composition of this embodiment can produce a film with an improved balance of release properties and heat resistance.

[0013] The reason why the effects of this embodiment are obtained is not entirely clear, but the following reasons can be inferred. It is thought that the resin composition of this embodiment allows for the creation of a film with an improved balance of release properties and heat resistance by introducing crosslinking groups into an olefin polymer (A) having release properties, and by allowing the crosslinking of the olefin polymer (A) to proceed appropriately through the catalytic action of the complex (B).

[0014] Next, the components of the resin composition will be described with specific examples. The resin composition of this embodiment includes an olefin polymer (A) having a crosslinkable group (hereinafter also referred to as polymer (A)) and a complex (B). The resin composition of this embodiment may consist of polymer (A) and complex (B), or it may contain components other than polymer (A) and complex (B). The resin composition of this embodiment may also include other components such as a hydrosilylation agent (C), a reaction inhibitor (D), a radical initiator, an olefin polymer other than polymer (A), an aromatic polymer, a fluororesin, etc., which will be described later. Each component will be described separately below.

[0015] <Complex (B)> The resin composition of this embodiment includes complex (B) from the viewpoint of obtaining a film with an improved balance of release properties and heat resistance. Furthermore, complex (B) includes a metal atom (B1) and a ligand (B2) from the viewpoint of obtaining a film with an improved balance of release properties and heat resistance.

[0016] 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).

[0017] 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.

[0018] 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 obtaining a film with a better balance of 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.

[0019] From the viewpoint of obtaining a film with a better balance of release properties and heat resistance, 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. 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.

[0020] Furthermore, the ligand (B2) preferably has an organosiloxane structure from the viewpoint of obtaining a film with an improved balance of 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.

[0021] 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 believed that in the film obtained with the resin composition of this embodiment, the catalytic function of complex (B) having a predetermined structure is exhibited to promote crosslinking of polymer (A), and the organosiloxane structure of complex (B) imparts release properties to the film. In other words, according to the resin composition of this embodiment, it is believed 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), resulting in a film with an improved balance of release properties and heat resistance.

[0022] Ligand (B2) includes a ligand represented by the following formula (L1) from the viewpoint of obtaining a film with a better balance of release properties and heat resistance. In other words, complex (B) includes a ligand represented by the following formula (L1).

[0023]

[0024] In equation (L1), n ​​represents a non-negative integer. Also, R １１ ~R １６each 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 to 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 20 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.

[0025] Examples of the organosiloxane group having 1 to 20 silicon atoms include a siloxy group, a modified siloxy group, and the like. The organosiloxane group having 1 to 20 silicon atoms includes an organosiloxane group in which a hydrogen atom in the organosiloxane group is partially substituted with a halogen atom such as fluorine. When the ligand represented by the formula (L1) has an organosiloxane group having 1 to 20 silicon atoms, the ligand represented by the formula (L1) may have a branched organosiloxane structure.

[0026] In formula (L1), n ​​is preferably an integer of 5 or less, more preferably an integer of 3 or less, and even more preferably an integer of 2 or less, from the viewpoint of obtaining a film with an improved balance of release properties and heat resistance.

[0027] R in equation (L1) １１ ~R １６ From the viewpoint of obtaining a film with a better balance of release properties and heat resistance, 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.

[0028] R in equation (L1) ２１ ~R ２４ From the viewpoint of obtaining a film with an improved balance of release properties and heat resistance, each of these is preferably one or more selected from the group consisting of hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, alkyl halides having 1 to 20 carbon atoms, and organosiloxane groups having 1 to 20 silicon atoms; more preferably one or more selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and phenyl groups; and even more preferably a methyl group.

[0029] In formula (L1), each X is independently selected from the group consisting of direct bonds and alkylene groups having 1 to 4 carbon atoms, from the viewpoint of obtaining a film with a better balance of release properties and heat resistance, preferably one or more selected from the group consisting of direct bonds, methylene groups and ethylene groups, and even more preferably direct bonds.

[0030] 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.

[0031] From the viewpoint of obtaining a film with improved release properties, the content of complex (B) in the resin composition of this embodiment is 0.0001 parts by mass or more, preferably 0.001 parts by mass or more, 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 composition of this embodiment is 100 parts by mass. From the viewpoint of reducing the decrease in heat resistance due to film embrittlement, the content of complex (B) in the resin composition of this embodiment is 5 parts by mass or less, preferably 4 parts by mass or less, 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 composition of this embodiment is 100 parts by mass. From the viewpoint of obtaining a film with an improved balance of release properties and heat resistance, the content of complex (B) in the resin composition of this embodiment is 0.0001 parts by mass or more and 5 parts by mass or less, 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.

[0032] From the viewpoint of obtaining a film with an improved balance of release properties and heat resistance, the content of complex (B) in the resin composition of this embodiment is preferably 0.0001% by mass or more and 5% by mass or less, more preferably 0.0001% by mass or more and 4% by mass or less, even more preferably 0.0001% by mass or more and 3% by mass or less, even more preferably 0.0001% by mass or more and 2% by mass or less, even more preferably 0.0001% by mass or more and 1% by mass or less, even more preferably 0.001% by mass or more and 0.8% by mass or less, even more preferably 0.005% by mass or more and 0.6% by mass or less, even more preferably 0.01% by mass or more and 0.5% by mass or less, and even more preferably 0.015% by mass or more and 0.4% by mass or less.

[0033] <Hydrosilylation agent (C)> The resin composition of this embodiment preferably further contains a hydrosilylation agent (C) from the viewpoint of obtaining a film with an improved balance of 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.

[0034] From the viewpoint of obtaining a film with a better balance of 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.

[0035] From the viewpoint of obtaining a film with a better balance of release properties and heat resistance, the hydrosilylation agent (C) preferably has a hydrosilyl group and a siloxane structure. The siloxane structure refers to a repeating structure of (-Si-O-) bonds.

[0036] From the viewpoint of obtaining a film with a better balance of release properties and heat resistance, the hydrosilylation agent (C) preferably includes a compound represented by the following formula (H1).

[0037]

[0038] 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, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an alkyl halide having 1 to 20 carbon atoms, or an organosiloxane group having 1 to 20 silicon atoms.

[0039] 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.

[0040] m in equation (H1) １ From the viewpoint of obtaining a film with an improved balance of 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.

[0041] m in equation (H1) ２ From the viewpoint of obtaining a film with an improved balance of 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.

[0042] m in equation (H1) １ +m ２From the viewpoint of obtaining a film with an improved balance of 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.

[0043] R in equation (H1) ３１ ~R ３９ From the viewpoint of obtaining a film with an improved balance of release properties and heat resistance, 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, 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.

[0044] From the viewpoint of obtaining a film with improved release properties, the content of the hydrosilylation agent (C) in the resin composition of this embodiment 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 polymer (A) in the resin composition of this embodiment is 100 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 polymer (A) in the resin composition of this embodiment is 10 even 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 polymer (A) in the resin composition of this embodiment is 100 parts by mass or less. The content of the hydrosilylation agent (C) in the resin composition of this embodiment 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, when the content of polymer (A) in the resin composition of this embodiment is 100 parts by mass.

[0045] From the viewpoint of obtaining a film with a better balance of release properties and heat resistance, the content of the hydrosilylation agent (C) in the resin composition of this embodiment 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.

[0046] From the viewpoint of obtaining a film with an improved balance of release properties and heat resistance, the content of the hydrosilylation agent (C) in the resin composition of this embodiment 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 composition (total amount of components remaining as solids when cured) is taken as 100% by mass.

[0047] <Olefin polymer (A) having crosslinkable groups> The resin composition of this embodiment includes polymer (A) from the viewpoint of obtaining a film with an improved balance of release properties and heat resistance. 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.

[0048] Polymer (A) has crosslinkable groups from the viewpoint of improving the heat resistance of the resulting cured product. 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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).

[0053] (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.

[0054] Polymer (A) includes copolymer (A1) from the viewpoint of obtaining a film with an improved balance of release properties and heat resistance. 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 containing repeating units derived from cyclic olefins.

[0055] The copolymer (A1) has crosslinkable groups from the viewpoint of improving the heat resistance of the resulting cured product. 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. The copolymer (A1) preferably contains vinyl groups from the viewpoint of obtaining a film with a better balance of release properties and heat resistance.

[0056] The copolymer (A1) preferably has a norbornene skeleton, from the viewpoint of obtaining a film with a better balance of 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.

[0057] (Composition of copolymer (A1)) Next, the repeating units of copolymer (A1) will be explained.

[0058] The copolymer (A1) includes repeating units (a1), repeating units (a2), and repeating units (a3) ​​from the viewpoint of obtaining a film with a better balance of 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.

[0059] 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).

[0060]

[0061] In equation (I), R ３００ This represents a hydrogen atom and a linear or branched alkyl group having 1 to 29 carbon atoms.

[0062]

[0063] 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.

[0064]

[0065] 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, 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.

[0066]

[0067] 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.

[0068]

[0069] 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.

[0070] 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 cycloalkyl groups having 3 to 15 carbon atoms include cyclopentyl and cyclohexyl 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 aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl, naphthyl, tolyl, xylyl, benzyl, and phenylethyl groups.

[0071] From the viewpoint of obtaining a film with a better balance of 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%.

[0072] From the viewpoint of obtaining a film with a better balance of 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%.

[0073] From the viewpoint of obtaining a film with a better balance of 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%.

[0074] (Raw materials for copolymer (A1)) Next, we will explain the raw materials for copolymer (A1).

[0075] Olefins, one of the raw materials for copolymer (A1), are monomers that undergo addition copolymerization to give repeating units (a1) represented by formula (I).

[0076] Examples of monomers that provide the repeating unit (a1) include olefins represented by the following formula (Ia) (hereinafter also referred to as olefin (Ia)).

[0077]

[0078] In equation (Ia), R ３００ This represents a hydrogen atom or a linear or branched alkyl group having 1 to 29 carbon atoms.

[0079] 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.

[0080] From the viewpoint of obtaining a film with a better balance of release properties and heat resistance, the olefin (Ia) preferably comprises one or more selected from the group consisting of ethylene and propylene, and more preferably comprises ethylene.

[0081] 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).

[0082] 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).

[0083]

[0084] 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.

[0085]

[0086] 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.

[0087]

[0088] 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.

[0089] 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.

[0090] The cyclic non-conjugated diene (IIa) preferably contains 5-ethylidene-2-norbornene, from the viewpoint of obtaining a film with a better balance of release properties and heat resistance.

[0091] 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.

[0092]

[0093]

[0094] From the viewpoint of obtaining a film with a better balance of 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.

[0095] 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.

[0096] From the viewpoint of obtaining a film with a better balance of release properties and heat resistance, the cyclic non-conjugated diene (IVa) preferably includes dicyclopentadiene.

[0097] 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.

[0098] 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).

[0099] 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)).

[0100]

[0101] 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.

[0102] 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.

[0103] From the viewpoint of obtaining a film with a better balance of 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).

[0104] (Other components of copolymer (A1)) Next, repeating units that copolymer (A1) may further contain will be described.

[0105] 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)).

[0106]

[0107] 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 ９９These elements may be bonded to each other to form monocyclic or polycyclic aromatic rings.

[0108]

[0109] 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.

[0110]

[0111] 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.

[0112] Examples of cyclic olefins (VIa) include cyclic olefin monomers described in International Publication No. 2006 / 118261.

[0113] Examples of cyclic olefins (VIIa) include cyclic olefin monomers described in International Publication No. 2006 / 118261.

[0114] 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.

[0115] From the viewpoint of obtaining a film with a better balance of release properties and heat resistance, the total content of repeating units (a6), (a7), and (a8) in the 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 the copolymer (A1) is taken as 100 mol%.

[0116] (Method for producing copolymer (A1)) Copolymer (A1) 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.

[0117] (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).

[0118]

[0119] 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 ６In 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 ~R ６ 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.

[0120] (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, from the viewpoint of obtaining a film with a better balance of release properties and heat resistance.

[0121] The number-average molecular weight Mn of polymer (A) is determined by the polymerization catalyst, co-catalyst, and H ２The 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).

[0122] From the viewpoint of obtaining a film with an improved balance of release properties and heat resistance, the content of polymer (A) in the resin composition of this embodiment 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 composition (total amount of components remaining as solids when cured) is taken as 100% by mass.

[0123] <Reaction Inhibitor (D)> The resin composition of this embodiment preferably further includes a reaction inhibitor (D) from the viewpoint of improving the moldability of the film. The reaction inhibitor (D) is, for example, a compound used to control the hydrosilylation reaction by a hydrosilylation agent (C).

[0124] 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.

[0125] 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 obtaining a film with a better balance of release properties and heat resistance.

[0126] From the viewpoint of obtaining a film with a better balance of release properties and heat resistance, the content of the reaction inhibitor (D) in the resin composition of this embodiment 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 polymer (A) in the resin composition of this embodiment 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 polymer (A) in the resin composition of this embodiment is 100 parts by mass or less, it may be, for example, 0 parts by mass or more, 0.001 parts by mass or more, or 0.01 parts by mass or more.

[0127] From the viewpoint of obtaining a film with a better balance of release properties and heat resistance, the content of the reaction inhibitor (D) in the resin composition of this embodiment 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 composition of this embodiment 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 composition of this embodiment is 100 parts by mass or less, it may be, for example, 0 parts by mass or more, 0.001 parts by mass or more, or 0.01 parts by mass or more.

[0128] <Other Components> The resin composition of this embodiment may contain other components as long as 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, mold 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.

[0129] (Fluorine-based resin) The resin composition of this embodiment 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-based resin monomer and a hydrocarbon-based resin monomer.

[0130] Examples of fully fluorinated resins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).

[0131] 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.

[0132] The content of the fluororesin in the resin composition of this embodiment 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 composition of this embodiment is 100 parts by mass or less.

[0133] The content of fluorine atoms in the resin composition of this embodiment 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 composition of this embodiment is 100 parts by mass.

[0134] (Aromatic Polymers) The resin composition of this embodiment 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 polyimide resins, aromatic polyamide resins, aromatic polyamide-imide resins, polydivinylbenzene, oligodivinylbenzene, isotactic polystyrene, syndiotactic polystyrene, atactic polystyrene, aromatic maleimide resins, modified phenylene ether resins, or resins modified from these resins.

[0135] (Olefin polymers other than polymer (A)) The resin composition of this embodiment 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.

[0136] In the resin composition of this embodiment, the content of olefin polymers other than polymer (A) 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, when the content of polymer (A) in the resin composition of this embodiment is 100 parts by mass or more and 1000 parts by mass or less.

[0137] (Aromatic Polyfunctional Monomers) The resin composition of this embodiment may further contain aromatic polyfunctional monomers. Aromatic polyfunctional monomers mean compounds 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.

[0138] From the viewpoint of obtaining a film with an improved balance of release properties and heat resistance, the content of aromatic polyfunctional monomers in the resin composition of this embodiment 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 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.

[0139] (Radical polymerization initiator) The resin composition of this embodiment may further contain a radical polymerization initiator. Examples of radical polymerization initiators include thermal radical polymerization initiators and photoradical 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 photoradical 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.

[0140] (Antioxidant) The resin composition of this embodiment may further contain an antioxidant. Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, thioether-based antioxidants, and hindered phenolic antioxidants.

[0141] The total content of polymer (A) and complex (B) in the resin composition of this embodiment 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 the resin composition (total amount of components remaining as solid matter when cured) is taken as 100% by mass.

[0142] <Method for preparing the resin composition> The resin composition of this embodiment can be prepared by mixing a polymer (A), a complex (B), and other components such as a hydrosilylation agent (C) and a reaction inhibitor (D) as needed. As a mixing method, a solution blending method, in which the components are dissolved or dispersed in a solvent, can be employed. 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.

[0143] The resin composition of this embodiment may be in an uncured or semi-cured state.

[0144] <Properties of the Resin Composition> The properties of the resin composition of this embodiment will be described below.

[0145] The resin composition of this embodiment has a peel strength P determined by the following (Method 1). ０ Explain.

[0146] Peel strength P ０ From the viewpoint of obtaining a film with an improved balance of 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.

[0147] (Method 1) A coated film is prepared by coating a 25 μm thick polyimide film with a varnish containing a resin composition. The coated film is then dried at 150°C for 4 minutes under an airflow with an oxygen concentration of 17 ± 3%, and then heated at 260°C for 10 minutes under an airflow with an oxygen concentration of 17 ± 3% to prepare a cured film with a thickness of 35 ± 5 μm. A 30 mm × 130 mm test piece is then prepared from the cured film. A 25 μm thick, 19 mm wide adhesive tape is then attached to the surface of the test piece on the side coated with varnish. The 90° peel strength is then 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.

[0148] Peel strength P ０ This can be adjusted, for example, by adjusting the composition of the resin composition, the conditions for preparing the resin composition, 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.

[0149] The resin composition of this embodiment has a peel strength P determined by the following (Method 2). １ Explain.

[0150] Peel strength P １ From the viewpoint of obtaining a film with an improved balance of 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. １The 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.

[0151] (Method 2) A coated film is prepared by coating a 25 μm thick polyimide film with a varnish containing a resin composition. The coated film is then dried at 150°C for 4 minutes under an airflow with an oxygen concentration of 17 ± 3%, and then heated at 260°C for 10 minutes under an airflow with an oxygen concentration of 17 ± 3% to prepare a cured film with a thickness of 35 ± 5 μm. A 30 mm × 130 mm test specimen is then prepared from the cured film. A structure is then prepared by sandwiching the test specimen 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 a small test press set to 30°C for 3 minutes. The test specimen is then removed from the structure. Next, an adhesive tape 25 μm thick and 19 mm wide is attached to the surface of the varnished test specimen. 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.

[0152] Peel strength P １ This can be adjusted, for example, by adjusting the composition of the resin composition, the conditions for preparing the resin composition, 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.

[0153] [Varnish] A varnish can be prepared by mixing the resin composition of this embodiment with a solvent. In other words, the varnish of this embodiment comprises the resin composition and a solvent.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] Methods for producing varnish include, for example, mixing a resin composition with a solvent. Apparatus for producing varnish includes, for example, a batch-type apparatus capable of stirring and mixing, and a continuous-type apparatus capable of stirring and mixing. The temperature during varnish production can be arbitrarily selected within the range from room temperature to the boiling point of the solvent. Alternatively, the reaction solution obtained when polymer (A) is acquired may be used directly to produce the varnish. For example, the method described in the examples can be used for producing the varnish.

[0159] [Cured Product] The cured product of this embodiment is a cured product of the resin composition of this embodiment. The cured product of this embodiment can be produced by crosslinking polymer (A) in the resin composition of this embodiment. The cured product can be produced, for example, by crosslinking the resin composition under conditions of a crosslinking temperature of 150°C or higher. Note that the crosslinking of polymer (A) may be carried out in the atmosphere 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.

[0160] 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.

[0161] The crosslinking reaction may be carried out with the resin composition of this embodiment in a molten state, or in a solution state in which the resin composition is dissolved or dispersed in a solvent. Alternatively, the crosslinking reaction may be carried out in the form of a film, sheet, etc. The formation of the film, sheet, etc., may be carried out, for example, by volatilizing the solvent or dispersion medium from the solution state. The method for producing the cured product can be, for example, the method described in the examples.

[0162] [Film] The film of this embodiment includes the resin composition of this embodiment or the cured product of this embodiment. By forming the resin composition or cured product into a film, the film can be used for various applications.

[0163] <Applications of the film> The applications of the film of this embodiment are not particularly limited, and the film of this embodiment can be applied to a variety of applications. The film of this embodiment is suitable as a release film because it has an improved balance of release properties and heat resistance. In particular, because the film of this embodiment has an improved balance of release properties and heat resistance, it is suitable as a release film used in semiconductor processes, release processes from molds used in the molding of structural members, high-bandwidth memory manufacturing processes, release processes for semiconductor encapsulants, and release processes in office automation equipment. Because the film of this embodiment has an improved balance of release properties and heat resistance, it is preferably used as a heat-resistant release film for the purpose of protecting chips and preventing adhesive contamination in the three-dimensional integration process of memory chips.

[0164] <Method for Manufacturing Film> As a method for forming a film from the resin composition or cured product of this embodiment, for example, a method in which the above-mentioned varnish is applied to a support substrate, dried, and then the resin composition is crosslinked to form a film made of the resin composition. Examples of support substrates include thermoplastic resin films such as PET film and polyimide film. As a method for applying the varnish to the support substrate, for example, an application using a coater is used. Examples of coaters include spin coaters, spray coaters, bar coaters, roll coaters, gravure coaters, small-diameter gravure coaters, reverse gravure coaters, and bank coaters. As a method for forming a film from the resin composition or cured product, for example, a method in which the resin composition is melt-formed and then crosslinked to form a cured product, thereby forming a film made of the resin composition. The method for manufacturing the film can be, for example, the method described in the examples.

[0165] [Laminated Film] The laminated film of this embodiment includes a base layer (a) and a resin layer (b) containing the film of this embodiment. That is, the laminated film has the resin layer (b) on at least one side of the base layer (a). From the viewpoint of reducing warping of the laminated film, the laminated film preferably has the resin layer (b) on both sides of the base layer (a). In this case, the laminated film has the base layer (a) between the two resin layers (b).

[0166] Next, the specific structure of the laminated film of this embodiment will be described with reference to the figures. Figure 1 schematically shows an example of the layer configuration of the laminated film (laminated film 100) of this embodiment.

[0167] The laminated film 100 comprises a base layer (a) 10 and a resin layer (b) 20 in this order. In other words, the laminated film 100 comprises a base layer (a) 10 and a resin layer (b) 20 on one side of the base layer (a) 10.

[0168] The overall thickness of the laminated film of 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.

[0169] Examples of the laminated film shape in this embodiment include film-like, sheet-like, and the like.

[0170] Next, specific examples of the components of the laminated film in this embodiment will be given.

[0171] <Base layer (a)> The 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 the base layer (a), the mechanical properties of the laminated film are improved, and the transportability and handling of the laminated film can be improved.

[0172] 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.

[0173] 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.

[0174] The base layer (a) may be a single layer or a layer consisting of two or more layers.

[0175] 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.

[0176] 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.

[0177] <Resin layer (b)> The resin layer (b) is a layer containing the film of this embodiment. In other words, the resin layer (b) is a layer containing the resin composition of this embodiment, or a cured product of the resin composition of this embodiment. The resin layer (b) is a layer that is positioned opposite to the electronic components when joining electronic components together by heat and pressure bonding (a layer positioned on the electronic component side), and is a layer provided to peel the laminated film from the electronic components after the electronic components have been heat and pressure bonded together.

[0178] The resin layer (b) may be a single layer or a layer consisting of two or more layers.

[0179] 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.

[0180] 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.

[0181] <Other Layers> The laminated film may include 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 the intermediate layer (c), adhesive layer, unevenness absorption layer, shock absorption layer, heat transfer layer, coating layer, etc., which will be described later.

[0182] <Intermediate layer (c)> The laminated film may further include an intermediate layer (c) between the substrate layer (a) and the resin layer (b). This improves the mechanical properties of the laminated 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.

[0183] <Applications of the Laminated Film> The applications of the laminated film of this embodiment are not particularly limited, and the laminated film of this embodiment can be applied to a variety of uses. In particular, since the laminated film of this embodiment has an improved balance of release properties and heat resistance, it is suitable as a heat-resistant release film used in semiconductor processes.

[0184] <Method for Manufacturing Laminated 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. For example, the method for manufacturing the laminated film can be the method described in the examples.

[0185] [Release Film] The release film of this embodiment includes the film of this embodiment or the laminated film of this embodiment. The release film of this embodiment is preferably used as a heat-resistant release film used in semiconductor processes.

[0186] 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).

[0187] Next, the specific structure of the release film of this embodiment will be described with reference to the figures. Figure 2 schematically shows an example of the layer configuration of the release film (release film 200) of this embodiment. Figure 3 schematically shows an example of the layer configuration when the release film (release film 200) of Figure 2 includes an intermediate layer (c) which will be described later.

[0188] The release film 200 in Figure 2 comprises a base layer (a) 10 and a resin layer (b) 20 in this order. That is, 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 3 comprises a base layer (a) 10, an intermediate layer (c) 30, and a resin layer (b) 20 in this order. That is, the release film 200 has an intermediate layer (c) 30 between the base layer (a) 10 and the resin layer (b) 20. Note that the release film 200 may be a laminated film 100, or it may be a combination of the film and base layer of this embodiment.

[0189] 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.

[0190] Examples of the release film shape in this embodiment include film-like or sheet-like forms.

[0191] 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.

[0192] 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.

[0193] 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).

[0194] The following materials were used in Comparative Examples 3 and 4, described later: • PTFE film (Product name: TOMBO9001 PTFE sheet, manufactured by Nichias Corporation) • PI film (Product name: UPILEX 25S, manufactured by UBE Corporation)

[0195] 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.

[0196] • Transition metal compound (1): Synthesized by the method described in Synthesis Example 1 of Japanese Patent Publication No. 2004-331965.

[0197] 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.)

[0198] Next, copolymers 1 to 4 were prepared using the following methods.

[0199] [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.

[0200] [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.

[0201] [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.

[0202] [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.

[0203] 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).

[0204] (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.

[0205] (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

[0206] Next, the preparation methods for each example and each comparative example will be described.

[0207] [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.

[0208] (Preparation of cured 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 conditions of an airflow with an oxygen concentration of 17±3%.

[0209] [Examples 2-15] Varnish and cured film 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.

[0210] [Comparative Examples 1-2] Varnish and cured film 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.

[0211] [Comparative Examples 3-4] In Comparative Example 3, a PTFE film was used instead of a cured film containing polymer (A). In Comparative Example 4, a PI film was used instead of a cured film containing polymer (A).

[0212] 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 cured films of Examples 1 to 15, the cured films of Comparative Examples 1 to 2, the PTFE film of Comparative Example 3, and the PI film of Comparative Example 4 may be collectively referred to as the "film of each example."

[0213] [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 (product name: Polyester Adhesive Tape No. 31B, manufactured by Nitto Denko Corporation) with a thickness of 25 μm and a width of 19 mm was attached to the surface of the varnished side of test piece 1. 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.

[0214] [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 side coated with varnish. 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.

[0215] [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.

[0216] [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.

[0217]

[0218] This application claims priority based on Japanese Patent Application No. 2024-199496, filed on 15 November 2024, and incorporates all of its disclosures herein.

[0219] 10 Base layer (a) 20 Resin layer (b) 30 Intermediate layer (c) 100 Laminated film 200 Release film

Claims

1. A resin composition comprising an olefin polymer (A) having a crosslinkable group and a complex (B), wherein the complex (B) comprises a metal atom and a ligand, and the content of the complex (B) is 0.0001 parts by mass or more and 5 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass.

2. The resin composition according to claim 1, 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.

3. The resin composition according to claim 1 or 2, 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 ~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, and 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 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 R １５ , R １４ and R １６ , R １５ and R １６ , R ２１ and R ２２ , R ２１ and R ２３ , R <矚 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. ] 4. The resin composition according to claim 1, further comprising a hydrosilylation agent (C) having a hydrosilyl group and a siloxane structure.

5. The resin composition according to claim 4, 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.

6. The resin composition according to claim 4 or 5, wherein the content of the hydrosilylated agent (C) is 0.01 parts by mass or more and 10 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass.

7. The resin composition according to claim 1 or 2, wherein the fluorine atom content is 50 parts by mass or less when the olefin polymer (A) content is 100 parts by mass.

8. The resin composition according to claim 1 or 2, wherein the olefin polymer (A) comprises a cyclic olefin copolymer (A1) having a crosslinkable group.

9. The cyclic olefin copolymer (A1) includes one or more repeating units (a2) selected from the group consisting of a repeating unit (a1) represented by the following formula (I), 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). The resin composition according to claim 8. [In the formula (I), R ３００ represents a hydrogen atom or a linear or branched alkyl group having 1 to 29 carbon atoms. ] [In the formula (II), u represents 0 or 1, v represents 0 or 1, w represents 0 or 1, and R ６１ to R ７６ , R ａ１ , and R ｂ１ each independently represent 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 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring. ] [In the formula (III), t represents an integer of 0 to 10, u represents 0 or 1, v represents 0 or a positive integer, w represents 0 or 1, and R ６１ to R ７６ , R ａ１ , and R ｂ１ each independently represent 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 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ７５ and R ７６ may be bonded to each other to form a monocyclic or polycyclic ring. ] [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 ７８ These may be bonded to each other to form a monocycle or polycycle.

10. The resin composition according to claim 9, wherein the olefin constituting the repeating unit (a1) contains ethylene.

11. 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 The resin composition according to claim 9, comprising one or more selected from the group consisting of ]-3-dodecene and 5-allyl-2-norbornene.

12. The cyclic olefin constituting the repeating unit (a3) ​​is tetracyclo[4.4.0.1 ２，５ 1. ７，１０ The resin composition according to claim 9, comprising one or more selected from the group consisting of ]-3-dodecene and bicyclo[2.2.1]-2-heptene.

13. The resin composition according to claim 1 or 2, further comprising a reaction inhibitor (D).

14. The resin composition according to claim 13, wherein the content of the reaction inhibitor (D) is 10 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass.

15. The resin composition according to claim 1 or 2, which is in an uncured or semi-cured state.

16. Peel strength P by the following (Method 1) ０ A resin composition according to claim 1 or 2, wherein the strength is 5.0 N / 19 mm or less. (Method 1) A coated film is prepared by coating a polyimide film with a thickness of 25 μm with a varnish containing the resin composition. The coated film is then dried at 150°C for 4 minutes under an airflow with an oxygen concentration of 17 ± 3%, and then heated at 260°C for 10 minutes under an airflow with an oxygen concentration of 17 ± 3% to prepare a cured film with a thickness of 35 ± 5 μm. A test piece measuring 30 mm × 130 mm is then prepared from the cured film. An adhesive tape measuring 25 μm thick and 19 mm wide is then attached to the surface of the test piece on the side coated with the varnish. The 90° peel strength is then 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.

17. Peel strength P by the following method (Method 2) １ The resin composition according to claim 1 or 2, wherein the ratio is 5.0 N / 19 mm or less. (Method 2) A coated film is prepared by coating a polyimide film with a thickness of 25 μm with a varnish containing the resin composition. The coated film is then dried at 150°C for 4 minutes under an airflow with an oxygen concentration of 17 ± 3%, and then heated at 260°C for 10 minutes under an airflow with an oxygen concentration of 17 ± 3% to prepare a cured film with a thickness of 35 ± 5 μm. A test piece measuring 30 mm × 130 mm is then prepared from the cured 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. Next, an adhesive tape 25 μm thick and 19 mm wide is attached to the surface of the test piece coated with the varnish. 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.

18. A cured product of the resin composition according to claim 1 or 2.

19. A film comprising the resin composition described in claim 1 or a cured product of the resin composition.

20. A laminated film comprising a base layer (a) and a resin layer (b) containing the film described in claim 19.

21. The laminated film according to claim 20, wherein the substrate 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.

22. The laminated film according to claim 20 or 21, wherein the thickness of the substrate layer (a) is 1 μm or more and 100 μm or less.

23. The laminated film according to claim 20 or 21, wherein the thickness of the resin layer (b) is 0.1 μm or more and 50 μm or less.

24. A release film comprising the film described in claim 19 or the laminated film described in claim 20.

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