Resin compositions, coating compositions, films, cured films, and laminates

Abstract

The present invention provides a resin composition that can produce a film with an improved balance of water repellency, oil repellency, and substrate adhesion properties. [Solution] A resin composition comprising an olefin polymer (A) having a crosslinkable group and a silane coupling agent (D) having one or more selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds.

Description

[Technical Field]

[0001] The present invention relates to resin compositions, coating compositions, films, cured films, and laminates. [Background technology]

[0002] From the viewpoint of imparting various functions to the surface of a laminate, for example, a functional film may be provided on the surface of the laminate. Examples of technologies related to functional membranes include the technologies described in Patent Documents 1 and 2.

[0003] Patent Document 1 discloses a perfluoro(poly)ether group-containing silane compound represented by a predetermined formula, with the objective of providing a novel perfluoro(poly)ether group-containing silane compound that can form a layer having water-repellent, oil-repellent, and stain-resistant properties, as well as high friction resistance.

[0004] Patent Document 2 discloses a method for producing a polymer thin film having water-repellent and oil-repellent properties, which has uniform physical properties and thickness throughout the entire region, while also having low average surface roughness and high durability and chemical resistance. The method includes the steps of: thermally decomposing a gaseous thermal initiator to form radicals; polymer synthesis, in which a monomer mixture containing a (meth)acrylate monomer substituted with a fluorine-based functional group and a reactive compound containing two or more vinyl groups or (meth)acrylate-based functional groups reacts with the formed radicals; and vapor deposition of the synthesized polymer onto a substrate, wherein the ratio of the vapor deposition partial pressure determined by a predetermined formula of the reactive compound containing two or more vinyl groups or (meth)acrylate-based functional groups to the vapor deposition partial pressure determined by a predetermined formula of the (meth)acrylate monomer substituted with a fluorine-based functional group is 0.10 to 0.80. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2024-028510 [Patent Document 2] Special Publication No. 2017-502167 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention provides a resin composition that can produce a film with an improved balance of water repellency, oil repellency, and substrate adhesion properties. [Means for solving the problem]

[0007] According to the present invention, the following resin compositions, coating compositions, films, cured films, and laminates are provided. [1] An olefin polymer (A) having a crosslinkable group, A resin composition comprising a silane coupling agent (D) having one or more selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds. [2] The resin composition according to [1], further comprising a complex (B) containing a metal atom and a ligand. [3] The resin composition according to [2], 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. [4] The resin composition according to [2] or [3], wherein the content of the complex (B) is 0.001 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. [5] The resin composition according to any one of [1] to [4], further comprising a hydrosilylation agent (C) having a hydrosilyl group and a siloxane structure. [6] The resin composition according to [5], wherein the hydrosilylation agent (C) comprises a compound represented by the following formula (H1). [Chemical formula] 〔In the above formula (H1), m1 represents a positive integer, m2 represents an integer of 0 or more, and R 31 ~R 39 each 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.〕 [7] The content of the hydrosilylation agent (C) is 0.1 part by mass or more and 200 parts by mass or less when the content of the olefin polymer (A) is 100 parts by mass, according to the resin composition described in [5] or [6] above. [8] The silane coupling agent (D) contains a compound represented by the following formula (S1), according to the resin composition described in any one of [1] to [7] above. [Chemical formula] 〔In the above formula (S1), R 41 ~R 43 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, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a siloxy group having 1 to 20 silicon atoms, and R 44 ~R 46 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, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and at least one of R 44 ~R 46 represents an alkoxy group having 1 to 20 carbon atoms, and R 47 represents a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a siloxy group having 1 to 20 silicon atoms.〕 [9] The resin composition according to any one of [1] to [8], wherein the content of the silane coupling agent (D) is 0.1 parts by mass or more and 200 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass.

[10] The resin composition according to any one of [1] to [9], wherein the olefin polymer (A) comprises a cyclic olefin copolymer (A1) having a crosslinkable group.

[11] The aforementioned cyclic olefin copolymer (A1) is The repeating unit (a1) is represented by the following formula (I), One or more repeating units (a2) 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), The resin composition according to

[10] , comprising a repeating unit (a3) ​​represented by the following formula (V). [ka] [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. [ka] [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. [ka] [In formula (III) above, t represents a positive 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. [ka] [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. [ka] [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 75and 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.

[12] The resin composition according to

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

[13] 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

[11] or

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

[14] 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 the above

[11] to

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

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

[14] , wherein the content of repeating units having crosslinkable groups in the olefin polymer (A) is 0.1 mol% or more and 60 mol% or less when the total content of repeating units in the olefin polymer (A) is 100 mol%.

[16] The resin composition according to any one of [1] to

[15] , wherein the fluorine atom content is 50 parts by mass or less when the content of the olefin polymer (A) is 100 parts by mass.

[17] A resin composition according to any one of the above [1] to

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

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

[17] , wherein the water contact angle by the following method (Method 1) is 85° or more. (Method 1) A coating solution is prepared by dissolving the resin composition in toluene, and then a resin film is formed on the SiO2 film formed on the surface of the substrate by spin-coating the coating solution onto the SiO2 film, and then the substrate is placed in a contact angle measuring device, and then 18 μL of distilled water is dropped onto the resin film, and then the water contact angle is measured using the θ / 2 method with the contact angle measuring device.

[19] A resin composition according to any of [1] to

[18] above, wherein the oleic acid contact angle by the method described below (Method 2) is 20° or more. (Method 2) A coating solution is prepared by dissolving the resin composition in toluene, and then a resin film is formed on the SiO2 film formed on the surface of the substrate by spin-coating the coating solution onto the SiO2 film, and then the substrate is placed in a contact angle measuring device, and then 18 μL of oleic acid is dropped onto the resin film, and then the oleic acid contact angle is measured using the θ / 2 method with the contact angle measuring device.

[20] A resin composition according to any one of the above [1] to

[19] , used for a coating film. [twenty one] A resin composition according to any one of the above [1] to

[20] , which is used for one or more selected from the group consisting of a water-repellent film, an oil-repellent film, and an anti-reflective film. [twenty two] A coating composition comprising the resin composition described in any of the above [1] to

[21] and a solvent. [twenty three] A film comprising the resin composition described in any of the above [1] to

[21] . [twenty four] A cured film of the film described in

[23] above. [twenty five] A resin layer including the film described in

[23] above, or a cured film of the film, A laminate comprising a base material.

[26] The laminate according to

[25] , wherein the resin layer comprises one or more selected from the group consisting of a water-repellent layer, an oil-repellent layer, and an anti-reflective layer. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a resin composition that can produce a film with an improved balance of water repellency, oil repellency, and substrate adhesion properties. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic cross-sectional view showing an example of the structure of the laminate according to this embodiment. [Modes for carrying out the invention]

[0010] The present invention will be described below based on embodiments. In these embodiments, unless otherwise specified, "A~B" indicating a numerical range represents 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 cases of A, B, and both A and B. In this specification, when a group (atomic group) is not specified as substituted or unsubstituted, it includes both groups that do not contain substituents and groups that do. For example, "alkyl group" includes not only alkyl groups that do not contain substituents (unsubstituted alkyl groups) but also alkyl groups that do contain substituents (substituted alkyl groups). In this specification, the term "(meth)acrylic" refers to a concept that encompasses both acrylic and methacrylic. The same applies to similar terms 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-based 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 comprises an olefin polymer (A) having a crosslinkable group and a silane coupling agent (D) having one or more selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds. The resin composition of this embodiment, having the above-described structure, can produce a film with an improved balance of water repellency, oil repellency, and substrate adhesion properties.

[0013] Although the reason for obtaining the above effects is not clear, in the resin composition of this embodiment, the olefin polymer (A) has crosslinkable groups, which improves the interaction between the olefin polymer (A) and the silane coupling agent (D) having one or more selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds. Furthermore, it is thought that the interaction between the water-repellent and oil-repellent olefin polymer (A) and the substrate is improved via the silane coupling agent (D). From the above, it is considered that the resin composition of this embodiment can be used to obtain a film with an improved balance of water repellency, oil repellency, and substrate adhesion properties.

[0014] Next, we will explain the constituent components of the resin composition with specific examples. The resin composition of this embodiment comprises an olefin polymer (A) having a crosslinkable group (hereinafter also referred to as polymer (A)) and a silane coupling agent (D). The resin composition of this embodiment may consist of polymer (A) and silane coupling agent (D), or it may contain components other than polymer (A) and silane coupling agent (D). The resin composition of this embodiment preferably contains one or more components selected from the group consisting of complex (B) and hydrosilylation agent (C), which will be described later, as components other than polymer (A) and silane coupling agent (D). The following sections will explain each component separately.

[0015] <Silane coupling agent (D)> The resin composition of this embodiment includes a silane coupling agent (D) from the viewpoint of obtaining a film with an improved balance of water repellency, oil repellency, and substrate adhesion properties.

[0016] The silane coupling agent (D) of this embodiment has one or more selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds, and preferably has carbon-carbon double bonds, in order to obtain a film with an improved balance of water repellency, oil repellency, and substrate adhesion properties. The silane coupling agent (D) may have one or more carbon-carbon double bonds, one or more carbon-carbon triple bonds, or one or more carbon-carbon double bonds and one or more carbon-carbon triple bonds in a single molecule.

[0017] The silane coupling agent (D) of this embodiment preferably contains a compound represented by the following formula (S1) from the viewpoint of improving adhesion to the substrate.

[0018] [ka]

[0019] In equation (S1), R 41 ~R 43 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, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a siloxy group having 1 to 20 silicon atoms. Also, R 44 ~R 46 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, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, R 44 ~R 46At least one of them represents an alkoxy group with 1 to 20 carbon atoms. Also, R 47 This represents a direct bond, an alkylene group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, or a siloxy group with 1 to 20 silicon atoms.

[0020] R in equation (S1) 41 ~R 43 From the viewpoint of independently improving adhesion to the substrate, each of these 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, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a siloxy group having 1 to 20 silicon atoms; more preferably, one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; and even more preferably, a hydrogen atom.

[0021] R in equation (S1) 44 ~R 46 Each of these groups, independently of the viewpoint of improving adhesion to the substrate, 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, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon 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 an alkoxy group having 1 to 4 carbon atoms; even more preferably, an alkoxy group having 1 to 4 carbon atoms; and even more preferably, one or two selected from a methoxy group and an ethoxy group. R 44 ~R 46 At least one of these is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably one or two selected from a methoxy group and an ethoxy group.

[0022] R in equation (S1) 47From the viewpoint of improving adhesion to the substrate, it is preferably one or more selected from the group consisting of a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a siloxy group having 1 to 20 silicon atoms, more preferably one or more selected from the group consisting of a direct bond and an alkyl group having 1 to 20 carbon atoms, and even more preferably a direct bond.

[0023] From the viewpoint of improving adhesion to the substrate, the content of the silane coupling agent (D) in the resin composition of this embodiment is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, when the content of the polymer (A) in the resin composition of this embodiment is 100 parts by mass. From the viewpoint of reducing embrittlement of the resulting film, the content of the silane coupling agent (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 50 parts by mass or less, and even more preferably 25 parts by mass or less, when the content of the polymer (A) in the resin composition of this embodiment is 100 parts by mass. The content of the silane coupling agent (D) in the resin composition of this embodiment is preferably 0.1 parts by mass or more and 200 parts by mass or less, more preferably 1 part by mass or more and 150 parts by mass or less, even more preferably 5 parts by mass or more and 100 parts by mass or less, even more preferably 10 parts by mass or more and 50 parts by mass or less, and even more preferably 15 parts by mass or more and 25 parts by mass or less, when the content of polymer (A) in the resin composition of this embodiment is 100 parts by mass.

[0024] <Complex (B)> The resin composition of this embodiment preferably further contains complex (B) from the viewpoint of improving water repellency and oil repellency. Complex (B) of this embodiment contains a metal atom (B1) and a ligand (B2).

[0025] Examples of metal atoms (B1) include platinum group atoms (b1) and base metal atoms (b2), which will be discussed later. Examples of base metal atoms (b2) include iron, cobalt, nickel, and manganese. Furthermore, if 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, ligand (B3) is a compound appropriately selected in accordance with the base metal atom (b2).

[0026] The complex (B) of this embodiment 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 catalysts for such addition reactions include those composed of platinum group elements, such as platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Examples of catalysts for addition reactions include those composed of group 8 metals, group 8 metal complexes, and group 8 metal compounds of the periodic table. Furthermore, the catalyst for the addition reaction may be a base metal catalyst. Examples of base metal catalysts include iron-based catalysts, cobalt-based catalysts, and nickel-based catalysts.

[0027] Platinum group atoms (b1) are atoms of the platinum group elements. Examples of platinum group atoms (b1) include platinum, palladium, rhodium, ruthenium, osmium, and iridium. 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, from the viewpoint of improving water repellency and oil repellency, 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.

[0028] Ligand (B2) preferably has a total of two or more of one or more types selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds, from the viewpoint of improving water repellency and oil repellency. 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.

[0029] Furthermore, the ligand (B2) preferably has an organosiloxane structure from the viewpoint of improving water repellency and oil repellency. 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.

[0030] Ligand (B2) preferably has a total of two or more of one or more selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds, and has an organosiloxane structure, from the viewpoint of improving water repellency and oil repellency.

[0031] In the complex (B) of this embodiment, the combination of metal atom (B1) and ligand (B2) is not limited to the above. Examples of complexes (B) other than the combinations of metal atoms (B1) and ligands (B2) described above include hexachloroplatin(IV) acid, tetrachloroplatin(II) acid, chlorotris(triphenylphosphine)rhodium(I), and pentamethylcyclopentadienyltris(acetonitrile)ruthenium(II)hexafluorophosphate. When complex (B) includes a complex (B) other than the combinations of metal atoms (B1) and ligands (B2), the resin composition of this embodiment further includes a hydrosilylating agent (C) described later.

[0032] From the viewpoint of improving water repellency and oil repellency, the content of complex (B) in the resin composition of this embodiment is preferably 0.001 parts by mass or more and 10 parts by mass or less, more preferably 0.005 parts by mass or more and 8 parts by mass or less, even more preferably 0.01 parts by mass or more and 4 parts by mass or less, even more preferably 0.05 parts by mass or more and 2 parts by mass or less, and even more preferably 0.1 parts by mass or more and 1 part by mass or less.

[0033] <Hydrosilylating agent (C)> The resin composition of this embodiment preferably further contains a hydrosilylation agent (C) from the viewpoint of improving water repellency and oil repellency. The hydrosilylation agent (C) is a compound that acts as a crosslinking agent. The hydrosilylation agent (C) may crosslink polymer (A) with silane coupling agent (D), or it may crosslink polymer (A) with other polymers (A). Hydrosilylation agents (C) have a hydrosilyl group (SiH group). In other words, hydrosilylation agents (C) have a hydrogen atom directly bonded to a silicon atom. As long as a hydrosilyl group is present, the molecular structure of a hydrosilylation agent (C) is not particularly limited. Examples of molecular structures of hydrosilylation agents (C) include linear, branched, cyclic, and three-dimensional network structures.

[0034] The hydrosilylation agent (C) of this embodiment preferably has two or more hydrosilyl groups, and more preferably three or more hydrosilyl groups, from the viewpoint of improving water repellency and oil repellency.

[0035] The hydrosilylated agent (C) of this embodiment preferably has a hydrosilyl group and a siloxane structure, from the viewpoint of improving water repellency and oil repellency. The siloxane structure refers to a repeating structure of (-Si-O-) bonds.

[0036] The hydrosilylation agent (C) of this embodiment preferably includes a compound represented by the following formula (H1) from the viewpoint of improving water repellency and oil repellency.

[0037] [ka]

[0038] In equation (H1), m1 represents a positive integer. Also, m2 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 with 1 to 20 silicon atoms include siloxy groups and modified siloxy groups. Organosiloxane groups with 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. If the compound represented by formula (H1) has an organosiloxane group with 1 to 20 silicon atoms, the compound represented by formula (H1) may also have a branched organosiloxane structure.

[0040] In formula (H1), m1 is preferably a positive integer, more preferably an integer between 2 and 1,000, and even more preferably an integer between 3 and 500, from the viewpoint of improving water repellency and oil repellency.

[0041] In formula (H1), m2 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, from the viewpoint of improving water repellency and oil repellency.

[0042] In formula (H1), m1 + m2 preferably represents 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, from the viewpoint of improving water repellency and oil repellency.

[0043] R in equation (H1) 31 ~R 39 Each of these components can independently improve water repellency and oil repellency, and 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] The content of the hydrosilylation agent (C) in the resin composition of this embodiment is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and even more preferably 20 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 efficiently promoting crosslinking and improving water repellency and oil repellency. From the viewpoint of reducing embrittlement of the resulting film, the content of the hydrosilylation agent (C) 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 120 parts by mass or less, even more preferably 100 parts by mass or less, and even more preferably 40 parts by mass or less, when the content of the polymer (A) in the resin composition of this embodiment is 100 parts by mass. The content of the hydrosilylation agent (C) in the resin composition of this embodiment is preferably 0.1 parts by mass or more and 200 parts by mass or less, more preferably 1 part by mass or more and 150 parts by mass or less, even more preferably 10 parts by mass or more and 120 parts by mass or less, even more preferably 15 parts by mass or more and 100 parts by mass or less, and even more preferably 20 parts by mass or more and 40 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 efficiently promoting crosslinking, improving water repellency and oil repellency, and reducing embrittlement of the resulting film.

[0045] <Olefin polymer having crosslinkable groups (A)> The resin composition of this embodiment includes polymer (A) from the viewpoint of obtaining a film with an improved balance of water repellency, oil repellency, and substrate adhesion. 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.

[0046] The polymer (A) of this embodiment has a crosslinkable group in order to obtain a film with an improved balance of water repellency, oil repellency, and substrate adhesion. The crosslinkable group includes, for example, one or more selected from the group consisting of vinyl group; vinylidene group; vinylene group; vinyl group substituted with alkyl group, phenyl group or alkylphenyl group; vinylidene group substituted with alkyl group, phenyl group or alkylphenyl group; vinylene group substituted with alkyl group, phenyl group or alkylphenyl group; maleimide group; thiol group; thienyl group; silyl group; epoxy group; oxazoline group; (meth)acrylic group; carboxyl group; and hydrosilyl group. Polymer (A) preferably contains vinyl groups from the viewpoint of obtaining a film with a better balance of water repellency, oil repellency, and substrate adhesion properties.

[0047] Examples of polymer (A) in this embodiment include a cyclic olefin copolymer (A1) having a crosslinkable group (hereinafter also referred to as copolymer (A1)), a cyclic olefin polymer (A2) having a crosslinkable group (hereinafter also referred to as polymer (A2)), an olefin homopolymer having a crosslinkable group, and an olefin copolymer having a crosslinkable group.

[0048] 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 members, or an alicyclic structure.

[0049] Examples of olefin-based homopolymers having crosslinkable groups include polydivinylbenzene, polybutadiene, and polydicyclopentadiene (dicyclopentadiene resin). Examples of olefin 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.

[0050] In this embodiment, the content of repeating units having crosslinkable groups in polymer (A) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, even more preferably 1 mol% or more, and even more preferably 5 mol% or more, when the total content of repeating units in polymer (A) is 100 mol%, from the viewpoint of improving the crosslink density. In this embodiment, the content of repeating units having crosslinkable groups in polymer (A) is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, and even more preferably 30 mol% or less, when the total content of repeating units in polymer (A) is 100 mol%, from the viewpoint of reducing embrittlement of the resulting film. In this embodiment, the content of repeating units having crosslinkable groups in polymer (A) is preferably 0.1 mol% to 60 mol%, more preferably 0.5 mol% to 50 mol%, even more preferably 1 mol% to 40 mol%, and even more preferably 5 mol% to 30 mol%, when the total content of repeating units in polymer (A) is 100 mol%, from the viewpoint of improving the crosslink density and reducing the embrittlement of the resulting film.

[0051] The polymer (A) of this embodiment preferably includes a cyclic olefin polymer, from the viewpoint of obtaining a film with an improved balance of water repellency, oil repellency, and substrate adhesion. Examples of cyclic olefin polymers include copolymer (A1) and polymer (A2).

[0052] (Cyclic olefin copolymer having crosslinkable groups (A1)) The polymer (A) of this embodiment will be described in detail below using copolymer (A1), but the polymer (A) of this embodiment is not limited to the following embodiments.

[0053] The polymer (A) of this embodiment includes copolymer (A1) from the viewpoint of obtaining a film with an improved balance of water repellency, oil repellency, and substrate adhesion. Examples of copolymer (A1) include thermosetting cyclic olefin copolymers and photocurable cyclic olefin copolymers. In addition, copolymer (A1) can be used without particular limitation as long as it is a copolymer containing repeating units derived from cyclic olefins.

[0054] The copolymer (A1) of this embodiment has a crosslinkable group in order to obtain a film with an improved balance of water repellency, oil repellency, and substrate adhesion. The crosslinkable group includes, for example, one or more selected from the group consisting of vinyl group; vinylidene group; vinylene group; vinyl group substituted with alkyl group, phenyl group or alkylphenyl group; vinylidene group substituted with alkyl group, phenyl group or alkylphenyl group; vinylene group substituted with alkyl group, phenyl group or alkylphenyl group; maleimide group; thiol group; thienyl group; silyl group; epoxy group; oxazoline group; (meth)acrylic group; carboxyl group; and hydrosilyl group. The copolymer (A1) preferably contains vinyl groups from the viewpoint of obtaining a film with a better balance of water repellency, oil repellency, and substrate adhesion properties.

[0055] Next, the repeating units of the copolymer (A1) in this embodiment will be described.

[0056] The copolymer (A1) of this embodiment includes repeating units (a1), repeating units (a2), and repeating units (a3) ​​from the viewpoint of obtaining a film with an improved balance of water repellency, oil repellency, and substrate adhesion properties. The repeating unit (a1) is a repeating unit represented by the following formula (I). In other words, the repeating unit (a1) is a repeating unit derived from one or more olefins. The repeating unit (a2) is one or more repeating units selected from the group consisting of the repeating units represented by formula (II), formula (III), and formula (IV) below. In other words, the repeating unit (a2) is a repeating unit derived from one or more cyclic non-conjugated dienes. The repeating unit (a3) ​​is a repeating unit represented by the following formula (V). In other words, the repeating unit (a3) ​​is a repeating unit derived from one or more cyclic olefins.

[0057] In the following, the repeating unit represented by equation (II) will also be called the repeating unit (a22). Similarly, the repeating unit represented by equation (III) will also be called the repeating unit (a23). Furthermore, the repeating unit represented by equation (IV) will also be called the 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).

[0058] [ka]

[0059] In equation (I), R 300 This represents a hydrogen atom and a linear or branched alkyl group having 1 to 29 carbon atoms.

[0060] [ka]

[0061] 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, an alkyl halide 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, an alkyl halide 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.

[0062] [ka]

[0063] In equation (III), t represents a positive integer between 0 and 10. Also, u represents 0 or 1. Also, v represents 0 or a positive integer. Also, w represents 0 or 1. Also, R 61 ~R 76 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide 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, an alkyl halide 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.

[0064] [ka]

[0065] 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, an alkyl halide 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 b1Each 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 may be bonded to each other to form a monocyclic or polycyclic ring.

[0066] [Chemical formula]

[0067] In formula (V), 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 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 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 may be bonded to each other to form a monocyclic or polycyclic ring.

[0068] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, etc. Examples of cycloalkyl groups having 3 to 15 carbon atoms include cyclopentyl groups and cyclohexyl groups. Furthermore, examples of alkyl halides having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms in which one or more halogen atoms substitute for hydrogen atoms. Furthermore, examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl, naphthyl, tolyl, xylyl, benzyl, and phenylethyl groups.

[0069] In this embodiment, the content of repeating units (a1) in the copolymer (A1) is preferably 10 mol% to 80 mol%, more preferably 30 mol% to 75 mol%, and even more preferably 50 mol% to 70 mol%, when the total content of repeating units in the copolymer (A1) is 100 mol%, from the viewpoint of obtaining a film with an improved balance of water repellency, oil repellency, and substrate adhesion.

[0070] In this embodiment, the content of repeating units (a2) in the copolymer (A1) is preferably 1 mol% to 60 mol%, more preferably 3 mol% to 50 mol%, even more preferably 5 mol% to 40 mol%, and even more preferably 8 mol% to 30 mol%, when the total content of repeating units in the copolymer (A1) is 100 mol%, from the viewpoint of obtaining a film with a better balance of water repellency, oil repellency, and substrate adhesion.

[0071] In this embodiment, the content of repeating units (a3) ​​in the copolymer (A1) is preferably 1 mol% to 50 mol%, more preferably 3 mol% to 45 mol%, even more preferably 5 mol% to 40 mol%, and even more preferably 8 mol% to 38 mol%, when the total content of repeating units in the copolymer (A1) is 100 mol%, from the viewpoint of obtaining a film with a better balance of water repellency, oil repellency, and substrate adhesion.

[0072] Next, the raw materials for copolymer (A1) of this embodiment will be described.

[0073] Olefins, one of the raw materials for copolymer (A1), are monomers that undergo addition copolymerization to give repeating units (a1) represented by formula (I).

[0074] Examples of monomers that provide the repeating unit (a1) include olefins represented by the following formula (Ia) (hereinafter also referred to as olefin (Ia)).

[0075] [ka]

[0076] In equation (Ia), R 300 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 29 carbon atoms.

[0077] 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. Furthermore, olefin (Ia) may be an olefin derived from biomass or an olefin derived from chemical recycling. Examples of biomass-derived olefins include biomass-derived ethylene and biomass-derived propylene.

[0078] Olefin (Ia) preferably contains one or more selected from the group consisting of ethylene and propylene, more preferably contains ethylene, from the viewpoint of obtaining a film having a better balance of water repellency, oil repellency, and substrate adhesion performance.

[0079] The cyclic non-conjugated diene, which is one of the raw materials of the 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 the repeating unit (a22) represented by the formula (II), the repeating unit (a23) represented by the formula (III), and the repeating unit (a24) represented by the formula (IV).

[0080] Examples of the monomer that gives the repeating unit (a22) include, for example, the cyclic non-conjugated diene represented by the following formula (IIa) (hereinafter also referred to as cyclic non-conjugated diene (IIa)). Examples of the monomer that gives the repeating unit (a23) include, for example, the cyclic non-conjugated diene represented by the following formula (IIIa) (hereinafter also referred to as cyclic non-conjugated diene (IIIa)). Examples of the monomer that gives the repeating unit (a24) include, for example, the cyclic non-conjugated diene represented by the following formula (IVa) (hereinafter also referred to as cyclic non-conjugated diene (IVa)). That is, examples of the monomer that gives the repeating unit (a2) include cyclic non-conjugated diene (IIa), cyclic non-conjugated diene (IIIa), cyclic non-conjugated diene (IVa), and the like.

[0081]

Chemical formula

[0082] In the formula (IIa), u represents 0 or 1. Also, v represents 0 or 1. Also, w represents 0 or 1. Also, R 61 ~R 76Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide 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, an alkyl halide 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.

[0083] [ka]

[0084] In equation (IIIa), t represents a positive integer between 0 and 10. Also, u represents 0 or 1. Also, v represents 0 or a positive integer. Also, w represents 0 or 1. Also, R 61 ~R 76 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide 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, an alkyl halide 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.

[0085] [ka]

[0086] 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, an alkyl halide 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, an alkyl halide 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.

[0087] 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 7,10 Examples include ]-3-dodecene. Furthermore, 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.

[0088] From the viewpoint of obtaining a film with a better balance of water repellency, oil repellency, and substrate adhesion properties, the cyclic non-conjugated diene (IIa) preferably includes 5-ethylidene-2-norbornene.

[0089] 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.

[0090] [ka]

[0091] [ka]

[0092] From the viewpoint of obtaining a film with a better balance of water repellency, oil repellency, and substrate adhesion properties, 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.

[0093] 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. Furthermore, 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.

[0094] From the viewpoint of obtaining a film with a better balance of water repellency, oil repellency, and substrate adhesion properties, the cyclic non-conjugated diene (IVa) preferably includes dicyclopentadiene.

[0095] From the viewpoint of obtaining a film with a better balance of water repellency, oil repellency, and substrate adhesion properties, the cyclic non-conjugated diene constituting the repeating unit (a2) is preferably 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, or 8-vinyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 It comprises one or more selected from the group consisting of ]-3-dodecene and 5-allyl-2-norbornene, more 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.

[0096] The copolymer (A1) can contain double bonds in its side chain portion by including repeating units (a2). Here, the side chain portion refers to the portion of copolymer (A1) other than the main chain.

[0097] 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).

[0098] 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)).

[0099] [ka]

[0100] 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 78Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide 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, an alkyl halide 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.

[0101] Examples of cyclic olefins (Va) include cyclic olefin monomers described in International Publication No. 2006 / 118261. Furthermore, the cyclic olefin (Va) may be a cyclic olefin derived from biomass, or a cyclic olefin derived from chemical recycling.

[0102] From the viewpoint of obtaining a film with a better balance of water repellency, oil repellency, and substrate adhesion properties, cyclic olefins (Va) are preferably tetracyclo[4.4.0.1 2,5 .1 7,10 It contains 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).

[0103] Next, we will describe the repeating units that the copolymer (A1) of this embodiment may further contain.

[0104] The copolymer (A1) of this embodiment may include repeating units other than repeating unit (a1), repeating unit (a2), and repeating unit (a3). Examples of repeating units other than repeating units (a1), (a2), and (a3) ​​include repeating units (a6) derived from a cyclic olefin represented by formula (VIa) (hereinafter also referred to as cyclic olefin (VIa)), repeating units (a7) derived from a cyclic olefin represented by formula (VIIa) (hereinafter also referred to as cyclic olefin (VIIa)), and repeating units (a8) derived from a linear polyene represented by formula (VIIIa) (hereinafter also referred to as linear polyene (VIIIa)).

[0105] [ka]

[0106] In equation (VIa), x and d are integers greater than or equal to 0. Also, y and z are integers between 0 and 2 (inclusive). 81 ~R 99 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. Also, R 89 and R 90 They may be bonded to each other to form a monoring or polyring. Also, when both y and z are 0, R 95 and R 92 or R 95 and R 99 These elements may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0107] [ka]

[0108] In equation (VIIa), R 100 and R 101 Each of these independently represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. Also, f represents an integer between 1 and 18.

[0109] [ka]

[0110] 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.

[0111] Examples of cyclic olefins (VIa) include cyclic olefin monomers described in International Publication No. 2006 / 118261.

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

[0113] 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, 4,8-dimethyl-1,4,8-decatriene (DMDT), 1,3-butadiene, and 1,5-hexadiene.

[0114] From the viewpoint of obtaining a film with an improved balance of water repellency, oil repellency, and substrate adhesion, the total content of repeating units (a6), (a7), and (a8) in the copolymer (A1) of this embodiment 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) of this embodiment is taken as 100 mol%.

[0115] (Method for manufacturing copolymer (A1)) The copolymer (A1) of this embodiment can be produced, for example, according to the method for producing a cyclic olefin copolymer described in paragraphs 0075 to 0219 of International Publication No. 2012 / 046443. The method for producing the copolymer (A1) in this embodiment can be, for example, the method described in the example.

[0116] (Copolymerization catalyst) In the method for producing the copolymer (A1) of this embodiment, for example, a copolymer catalyst can be used. Examples of copolymer 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 copolymer catalyst preferably contains a transition metal compound, and more preferably contains a transition metal compound represented by the following formula (X).

[0117] [ka]

[0118] In formula (X), m is an integer from 1 to 4. Also, n is a number that satisfies the valency of Ti. Furthermore, R1 to R5 each independently represent 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. Furthermore, R6 represents an aliphatic hydrocarbon group in which the carbon atom bonded to the phenyl group in formula (X) is a primary, secondary, or tertiary carbon atom; an alicyclic hydrocarbon group in which the carbon atom bonded to the phenyl group in formula (X) is a primary, secondary, or tertiary carbon atom; or an aromatic group. Furthermore, 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 equation (X), if m is 2 or greater, one of the R1-R6 groups in one ligand may be linked to one of the R1-R6 groups in another ligand. However, R1 groups cannot be linked to each other. Also, R1 groups, R2 groups, R3 groups, R4 groups, R5 groups, and R6 groups may be identical or different from each other. In equation (X), when n is 2 or greater, the multiple groups represented by X may be identical or different from each other. Furthermore, the multiple groups represented by X may be bonded together to form a ring.

[0119] <Other ingredients> The resin composition of this embodiment may contain other components, as long as they do not impede the effects of the invention of this embodiment. Examples of other components include resins other than polymer (A), additives, and so on. Examples of resins other than polymer (A) include fluoropolymers; 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 reaction inhibitors, aromatic polyfunctional monomers, radical polymerization initiators, antioxidants, inorganic fillers, organic fillers, heat stabilizers, weather stabilizers, radiation stabilizers, plasticizers, lubricants, mold release agents, nucleating agents, friction and 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, and defoaming agents. Here, reaction inhibitors are compounds used to control hydrosilylation reactions.

[0120] (Fluorine-based resin) The resin composition of this embodiment may further contain a fluororesin. Examples of fluoropolymer resins include fully fluorinated resins and partially fluorinated resins. Fully fluorinated resins refer to resins in which all hydrogen atoms in the molecule are replaced with fluorine atoms. Partially fluorinated resins refer to resins in which some of the hydrogen atoms in the molecule are replaced with fluorine atoms, or copolymers of fluoropolymer monomers and hydrocarbon-based resin monomers.

[0121] Examples of fully fluorinated resins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).

[0122] 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.

[0123] From the viewpoint of improving process suitability and environmental compatibility, the content of 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. In this embodiment, "improving process suitability" means increasing the number of processes to which it can be applied.

[0124] From the viewpoint of improving process suitability and environmental compatibility, the fluorine atom content 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 polymer (A) content in the resin composition of this embodiment is 100 parts by mass. Furthermore, the fluorine atom content in the resin composition can be expressed as the mass of fluorine atoms in the resin composition.

[0125] <Method for preparing resin compositions> The resin composition of this embodiment can be prepared by mixing a polymer (A), a silane coupling agent (D), and, if necessary, other components such as a complex (B) and a hydrosilylation agent (C). 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 linear saturated hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and ketones. Examples of linear saturated hydrocarbons include heptane, hexane, and decane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene, benzene, and xylene. Examples of ketones include cyclohexanone.

[0126] The resin composition of this embodiment may be in an uncured or semi-cured state.

[0127] <Properties of resin compositions> The properties of the resin composition of this embodiment will be described below.

[0128] The water contact angle for the resin composition of this embodiment will be explained below (Method 1).

[0129] From the viewpoint of improving water repellency, the water contact angle is preferably 85° or higher, more preferably 90° or higher, even more preferably 95° or higher, and even more preferably 100° or higher. There is no particular upper limit to the water contact angle, but for example, it may be 150° or less, 140° or less, 130° or less, or 120° or less.

[0130] (Method 1) A coating solution is prepared by dissolving the resin composition in toluene. Next, a resin film is formed on the SiO2 film formed on the surface of the substrate by spin-coating the coating solution onto the SiO2 film. Then, the substrate is placed in a contact angle measuring device. Next, 18 μL of distilled water is dropped onto the resin film. Finally, the water contact angle is measured using the θ / 2 method with the contact angle measuring device.

[0131] The oleic acid contact angle for the resin composition of this embodiment will be explained below (Method 2).

[0132] From the viewpoint of improving oil repellency, the oleic acid contact angle is preferably 20° or more, more preferably 25° or more, even more preferably 30° or more, even more preferably 35° or more, even more preferably 40° or more, even more preferably 45° or more, and even more preferably 50° or more. There is no particular upper limit to the oleic acid contact angle; for example, it may be 100° or less, 95° or less, or 90° or less.

[0133] (Method 2) A coating solution is prepared by dissolving the resin composition in toluene. Next, a resin film is formed on the SiO2 film formed on the surface of the substrate by spin-coating the coating solution onto the SiO2 film. Then, the substrate is placed in a contact angle measuring device. Next, 18 μL of oleic acid is dropped onto the resin film. Finally, the oleic acid contact angle is measured using the θ / 2 method with the contact angle measuring device.

[0134] <Uses of resin compositions> The applications of the resin composition of this embodiment are not particularly limited, and the resin composition of this embodiment can be applied to a variety of uses. The resin composition of this embodiment is suitable for use in coating films, for example, because it can produce a film with an improved balance of water repellency, oil repellency, and adhesion to the substrate. Examples of coating films include coating films formed on a substrate. Examples of substrates include resins, metals, inorganic compounds such as glass and ceramics, composites such as glass and ceramic composite compositions, or laminates in which one or more films are formed on the surface of these materials. Examples of laminates include molded bodies such as lenses, displays, and automotive sensors. In particular, the resin composition of this embodiment is suitable for use as a coating film for in-vehicle sensors or a coating film for molded bodies. Examples of molded bodies include optical molded bodies. Examples of optical molded bodies include lenses and mirrors.

[0135] The applications of the coating film using the resin composition of this embodiment are not particularly limited. Since the resin composition of this embodiment can produce a film with an improved balance of water repellency, oil repellency, and substrate adhesion, it can be used, for example, for one or more coating films selected from the group consisting of water-repellent films, oil-repellent films, and anti-reflective films.

[0136] [Compositions for coatings] The coating composition of this embodiment comprises a resin composition and a solvent. The coating composition of this embodiment can be prepared, for example, by further adding a solvent to the resin composition of this embodiment.

[0137] The solvent included in the coating composition is not particularly limited as long as it does not impair the solubility or affinity of the polymer (A), complex (B), hydrosilylater (C), and silane coupling agent (D). Examples of solvents used in the coating composition include linear saturated hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, ketones, cellosolves, esters, halogenated hydrocarbons, and ethers.

[0138] Examples of straight-chain 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, acetophenone, and 4-methyl-2-pentanone. 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.

[0139] The solvent used in the coating composition preferably comprises one or more selected from the group consisting of heptane, decane, cyclohexane, methylcyclohexane, decahydronaphthalene, toluene, benzene, xylene, mesitylene, pseudocumene, cyclohexanone, methyl ethyl ketone, and 4-methyl-2-pentanone, 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.

[0140] The solvent content in the coating composition of this embodiment can be adjusted according to the coating method and the film thickness to be formed. For example, when forming a thin film with a thickness of 100 nm or less by spin coating, the solvent content in the coating composition is preferably 10,000 parts by mass or more and 100,000 parts by mass or less, more preferably 20,000 parts by mass or more and 90,000 parts by mass or less, and even more preferably 40,000 parts by mass or more and 50,000 parts by mass or less, when the polymer (A) content in the coating composition is 100 parts by mass, from the viewpoint of improving the balance between the handling and coating properties of the coating composition.

[0141] Methods for preparing coating compositions include, for example, mixing a resin composition with a solvent. Apparatus for preparing coating compositions includes, for example, batch-type apparatus capable of stirring and mixing, and continuous-type apparatus capable of stirring and mixing. The temperature during preparation of the coating composition can be arbitrarily selected within the range from room temperature to the boiling point of the solvent.

[0142] [film] The film of this embodiment includes the resin composition of this embodiment. The film of this embodiment can be produced by coating the resin composition onto a substrate. The film of this embodiment may be, for example, a thin film with a thickness of 100 nm or less.

[0143] The method for coating the resin composition is not particularly limited. Examples of coating methods include spin coating, dip coating, spray coating, die coating, flow coating, curtain coating, bar coating, roll coating, and gravure coating.

[0144] The cured film of this embodiment is obtained by curing the film of this embodiment. The cured film can be produced by crosslinking the film of this embodiment. The heating temperature for promoting crosslinking is, for example, 60°C or higher. The heating temperature for promoting crosslinking can be adjusted according to the heat resistance of the substrate, as long as it is 60°C or higher. Furthermore, the film crosslinking may be carried out in air or in an inert atmosphere. Examples of inert atmospheres include nitrogen and argon. Furthermore, the film crosslinking may be carried out under normal pressure or under reduced pressure.

[0145] <Applications of the membrane> The application of the film of this embodiment is not particularly limited, and the film of this embodiment can be applied to a variety of uses. The film of this embodiment has an improved balance of water repellency, oil repellency, and substrate adhesion, making it suitable for use as a coating film on laminates, for example. In particular, the film of this embodiment is suitable for use as a coating film on molded bodies. Because the film of this embodiment has an improved balance of water repellency, oil repellency, and substrate adhesion properties, it can be used, for example, as one or more coating films selected from the group consisting of water-repellent films, oil-repellent films, and anti-reflective films.

[0146] [Laminated structure] The laminate of this embodiment comprises a substrate (a) and a resin layer (b) containing the film of this embodiment or its cured film. In other words, the laminate has the resin layer (b) on at least one side of the substrate (a). The laminate may have a resin layer (b) on only one side of the substrate (a), or it may have a resin layer (b) on both sides of the substrate (a).

[0147] Next, the specific structure of the laminate of this embodiment will be described with reference to the figures. Figure 1 schematically shows an example of the layer configuration of the laminate (laminated body 100) of this embodiment.

[0148] The laminate of this embodiment comprises a base material (a) 10 and a resin layer (b) 20 in this order. In other words, the laminate 100 comprises a base material (a) 10 and a resin layer (b) 20 on one side of the base material (a) 10.

[0149] The overall thickness of the laminate in this embodiment, the thickness of each layer, and the overall shape can be adjusted as appropriate depending on the application of the laminate.

[0150] The material of the base material is not particularly limited. Examples of base material materials include resins; metals; inorganic compounds such as glass and ceramics; composites such as glass and ceramic composite compositions; or laminates in which one or more films are formed on the surface of these materials. The substrate (a) may be a single layer or a layer consisting of two or more layers.

[0151] The substrate (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.

[0152] <Resin layer (b)> The resin layer (b) is a layer containing the film of the present embodiment or its cured film. That is, the resin layer (b) is a layer containing the resin composition of the present embodiment or the cured product of the resin composition of the present embodiment.

[0153] The resin layer (b) may be a single layer or a layer composed of two or more kinds of layers. The resin layer (b) contains, for example, one or two or more kinds selected from the group consisting of a water-repellent layer, an oil-repellent layer, and an antireflection layer.

[0154] The thickness of the resin layer (b) is appropriately determined according to the use of the laminate. For example, when the laminate is an optical molded body and the resin layer (b) is a water-repellent layer, the thickness of the resin layer (b) may be 100 nm or less.

[0155] The resin layer (b) may be surface-treated in order to improve the adhesiveness with other layers. Examples of the surface treatment include corona treatment, plasma treatment, undercoat treatment, primer coat treatment, and the like.

[0156] <Other layers> The laminate may include a layer other than the base material (a) and the resin layer (b). Examples of the layer other than the base material (a) and the resin layer (b) include an intermediate layer, an adhesive layer, a concavo-convex absorption layer, a shock absorption layer, a heat transfer layer, a coating layer, and the like. The other layers may be a single layer or a layer composed of two or more kinds of layers.

[0157] <Use of the laminate> The use of the laminate of the present embodiment is not particularly limited, and the laminate of the present embodiment can be applied to various uses.

[0158] <Manufacturing method of the laminate> Examples of the manufacturing method of the laminated film of the present embodiment include a method of coating the resin layer (b) on the base material (a). The manufacturing method of the laminate can be selected according to the type of the base material (a), the type of the resin layer (b), and the like.

[0159] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that do not impair the effects of the present invention are included in the present invention. [Examples]

[0160] 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.

[0161] First, let's explain the components used in each example. ·Polymer (A) (Copolymer (A1)) Copolymer 1: Synthesis Example 1 described below (content of repeating unit (a1) is 62 mol%, content of repeating unit (a2) is 27 mol%, content of repeating unit (a3) ​​is 11 mol%) Copolymer 2: Synthesis example 2 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%) • Complex (B) Platinum complex 1: 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) • Hydrosilylated agent (C) Hydrosilylation agent 1: Hydrosilyl group-containing compound (trimethylsiloxy-terminated methylhydrogensiloxane, CAS number: 63148-57-2) (hereinafter also referred to as HS agent 1). Hydrosilylation agent 2: Hydrosilyl group-containing compound (phenyltris(dimethylsiloxy)silane, CAS number: 18027-45-7) (hereinafter also referred to as HS agent 2). • Silane coupling agent (D) Vinyltrimethoxysilane (CAS number: 2768-02-7) (hereinafter also referred to as SC agent 1). • Silane coupling agents other than silane coupling agent (D) 3-aminopropyltrimethoxysilane (CAS No.: 13822-56-5) (hereinafter also referred to as SC agent 2). · Solvent Toluene (dehydrated toluene, manufactured by Kanto Chemical Co., Inc.)

[0162] Next, the production methods of copolymers 1 to 2 and the measurement methods of the physical properties (content of each repeating unit) of copolymers 1 to 2 will be described. First, the production methods of copolymers 1 to 2 will be described. The following raw materials were used for the synthesis of copolymers 1 to 2.

[0163] Transition metal compound (1): Synthesized by the method described in Synthesis Example 1 of JP-A-2004-331965.

[0164] Modified methylaluminoxane (product name: MMAO-3A, manufactured by Tosoh Finechem Corporation) (hereinafter also referred to as MMAO). Ethylene (manufactured by Mitsui Chemicals, Inc.) ​​​​​​​​​​​​​​​​​​​​​​​​In a 1000 mL stainless steel autoclave with a volume of SUS (stainless steel) that had been thoroughly purged with nitrogen, 455 mL of toluene, 29 mL of VNB, 16 mL of TD, and MMAO hexane solution (0.8 mmol in terms of aluminum atoms) and 446 mL of hydrogen were added. Then, ethylene was added to the SUS 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 SUS 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 was complete, deionized water was added to the resulting solution and stirred for 1 hour, after which 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 containing the precipitated polymer was stirred and filtered through filter paper. The resulting polymer was then dried under reduced pressure at 80°C for 10 hours to obtain copolymer 1.

[0167] [Synthesis example 2: Copolymer 2] Copolymer 2 was obtained by adjusting the amount of each raw material and the reaction conditions compared to the synthesis procedure for copolymer 1.

[0168] Next, we will explain the method for measuring the physical properties of copolymers 1 and 2. The content of repeating units (a1), (a2), and (a3) ​​in copolymers 1 and 2 was measured according to the following (method for measuring the content of each repeating unit).

[0169] (Method for measuring the content of each repeating unit) Using a nuclear magnetic resonance spectrometer (product name: EXcalibur270, manufactured by JEOL Ltd.), copolymers 1 and 2 were analyzed. 1 The H-NMR spectra were measured for each. 1 1H-NMR measurements were performed with 16 to 64 cumulative cycles at room temperature of 25°C. obtained 1From the 1H-NMR spectrum, the content of repeating units (a1), (a2), and (a3) ​​was calculated based on the intensities of the peaks derived from hydrogen directly bonded to the double bond carbon and the peaks derived from other hydrogen atoms.

[0170] Next, the preparation methods for each example and each comparative example will be described.

[0171] [Example 1] (Preparation of coating compositions) Copolymer 1 and other components were weighed according to the formulations shown in Table 1. The weighed components were then stirred in the solvent until fully dissolved to obtain a coating composition. Note that the units for the proportions of each raw material in Table 1 are parts by mass. Also, the mass of complex (B) is the mass of the entire solution.

[0172] (Fabrication of laminates) A substrate 1 (a disc-shaped transparent substrate) with an SiO2 film formed on its surface to provide anti-reflective properties was prepared. Substrate 1 was placed in a tabletop spin coater (manufactured by ABLE). Next, a coating composition was spin-coated onto the SiO2 film to form a resin film on the SiO2 film and obtain a laminate. The spin-coating conditions were as follows: rotation at a speed of 500 rpm for a rotation time of 5 seconds, followed by continuous rotation at a speed of 1000 rpm for a rotation time of 10 seconds.

[0173] [Examples 2-4, Comparative Examples 1-3] Except for changing the formulation of the coating composition to the formulation shown in Table 1 corresponding to each example, the coating composition and laminate were prepared in the same manner as in Example 1.

[0174] The properties of the resin film in the laminate were measured or evaluated according to the method described below. The results are shown in Table 1.

[0175] (Measurement of water contact angle) Each example of the laminate was placed in a contact angle measuring device (Solid Surface Energy Analyzer CA-XE, manufactured by Kyowa Interface Science Co., Ltd.). Next, 18 μL of distilled water was dropped onto the resin film in the laminate. Then, the water contact angle was measured using the θ / 2 method with the contact angle measuring device.

[0176] (Evaluation of substrate adhesion) The surface of the resin film in each laminate was subjected to 10 reciprocating friction cycles using a nonwoven fabric (BEMCOT M-3II, manufactured by Asahi Kasei Corporation) with a load of 10g or less. After the friction was completed, the laminate was visually inspected to see if delamination of the resin film had occurred. Cases where no delamination of the resin film was observed were evaluated as A, and cases where delamination of the resin film was observed were evaluated as B.

[0177] (Evaluation of the maintenance of anti-reflective properties) Each example of the laminate was placed under a fluorescent light. The surface with the resin film was visually inspected to determine whether it had anti-reflective properties. Cases with anti-reflective properties were rated A, and cases without anti-reflective properties were rated B.

[0178] (Measurement of oleic acid contact angle) Each laminate was placed in a contact angle measuring device (Solid Surface Energy Analyzer CA-XE, manufactured by Kyowa Interface Science Co., Ltd.). Next, 18 μL of oleic acid was dropped onto the resin film in the laminate. Then, the oleic acid contact angle was measured using the θ / 2 method with the contact angle measuring device.

[0179] [Table 1] [Explanation of symbols]

[0180] 10 Base material (a) 20 Resin layer (b) 100-layer structure

Claims

1. An olefin polymer (A) having a crosslinkable group, A resin composition comprising a silane coupling agent (D) having one or more selected from the group consisting of carbon-carbon double bonds and carbon-carbon triple bonds.

2. The resin composition according to claim 1, further comprising a complex (B) containing a metal atom and a ligand.

3. The resin composition according to claim 2, 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.

4. The resin composition according to claim 2 or 3, wherein the content of the complex (B) is 0.001 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.

5. The resin composition according to claim 1 or 2, further comprising a hydrosilylation agent (C) having a hydrosilyl group and a siloxane structure.

6. The resin composition according to claim 5, wherein the hydrosilylation agent (C) comprises a compound represented by the following formula (H1). 【Chemistry 1】 [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.

7. The resin composition according to claim 5, wherein the content of the hydrosilylated agent (C) is 0.1 parts by mass or more and 200 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass.

8. The resin composition according to claim 1 or 2, wherein the silane coupling agent (D) comprises a compound represented by the following formula (S1). 【Chemistry 2】 〔In the formula (S1), R ４１ ~R ４３ 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, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a siloxy group having 1 to 20 silicon atoms, and R ４４ ~R ４６ 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, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and at least one of R ４４ ~R ４６ represents an alkoxy group having 1 to 20 carbon atoms, and R ４７ represents a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a siloxy group having 1 to 20 silicon atoms.〕

9. The resin composition according to claim 1 or 2, wherein the content of the silane coupling agent (D) is 0.1 parts by mass or more and 200 parts by mass or less, when the content of the olefin polymer (A) is 100 parts by mass.

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

11. The cyclic olefin copolymer (A1) is The repeating unit (a1) is represented by the following formula (I), One or more repeating units (a2) 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), The resin composition according to claim 10, comprising a repeating unit (a3) ​​represented by the following formula (V). 【Transformation 3】 [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. 【Chemistry 4】 [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. 【Transformation 5】 [In formula (III) above, t represents a positive 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. 【Transformation 6】 [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. 【Transformation 7】 [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.

12. The resin composition according to claim 11, wherein the olefin constituting the repeating unit (a1) contains ethylene.

13. 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 11, comprising one or more selected from the group consisting of ]-3-dodecene and 5-allyl-2-norbornene.

14. 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 11, comprising one or two selected from the group consisting of ]-3-dodecene and bicyclo[2.2.1]-2-heptene.

15. The resin composition according to claim 1 or 2, wherein the content of repeating units having crosslinkable groups in the olefin polymer (A) is 0.1 mol% or more and 60 mol% or less when the total content of repeating units in the olefin polymer (A) is 100 mol%.

16. 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.

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

18. The resin composition according to claim 1 or 2, wherein the water contact angle by the following method (Method 1) is 85° or more. (Method 1) A coating solution is prepared by dissolving the resin composition in toluene, and then the SiO formed on the surface of the substrate ２ The resin film is formed by spin-coating the coating liquid onto the film with the SiO ２ The substrate is prepared on a film, then the substrate is placed on a contact angle measuring device, then 18 μL of distilled water is dropped onto the resin film, and then the water contact angle is measured using the θ / 2 method with the contact angle measuring device.

19. The resin composition according to claim 1 or 2, wherein the oleic acid contact angle by the method described below (Method 2) is 20° or more. (Method 2) A coating solution is prepared by dissolving the resin composition in toluene, and then the SiO formed on the surface of the substrate ２ The resin film is formed by spin-coating the coating liquid onto the film with the SiO ２ The substrate is prepared on a film, then the substrate is placed on a contact angle measuring device, then 18 μL of oleic acid is dropped onto the resin film, and then the oleic acid contact angle is measured using the θ / 2 method with the contact angle measuring device.

20. A resin composition according to claim 1 or 2, used in a coating film.

21. The resin composition according to claim 1 or 2, which is used for one or more selected from the group consisting of a water-repellent film, an oil-repellent film, and an anti-reflective film.

22. A coating composition comprising the resin composition according to claim 1 or 2 and a solvent.

23. A film comprising the resin composition according to claim 1 or 2.

24. A cured film of the film according to claim 23.

25. A resin layer comprising the film according to claim 23, or a cured film of the film, A laminate comprising a base material.

26. The laminate according to claim 25, wherein the resin layer comprises one or more selected from the group consisting of a water-repellent layer, an oil-repellent layer, and an anti-reflective layer.

Images