Composition, membrane, optical film and image display device

Abstract

The present invention addresses the problem of providing: a composition capable of forming a membrane having excellent anti-fouling properties; a membrane; an optical film; and an image display device. This composition contains an anti-fouling agent. The anti-fouling agent is a copolymer having: a repeating unit A derived from a hydrophobic monomer; and a repeating unit B that includes at least one structure selected from the group consisting of a polyalkylene oxide structure, a polyester structure, and a structure that includes two or more monocyclic aromatic rings. The weight-average molecular weight of the copolymer is 2,000-500,000.

Description

Compositions, films, optical films, and image display devices

[0001] The present invention relates to compositions, films, optical films, and image display devices.

[0002] Fluorine-containing compounds, particularly perfluoroalkyl compounds (PFAS), are known to have excellent properties such as water repellency and oil repellency, and are used in various fields. However, recently, due to their difficulty in decomposition, regulations on PFAS are progressing, and the use of alternative materials that do not use fluorine atoms is being considered.

[0003] As an alternative material, for example, Patent Document 1 describes a liquid repellent containing a silicone polymerizable resin ([Claim 1][Claim 8]).

[0004] Japanese Patent Publication No. 2023-169574

[0005] The present inventors investigated a composition containing a liquid repellent described in Patent Document 1 and found that the antifouling properties of the film (including the cured product of the composition) formed using the composition were poor.

[0006] Therefore, the object of the present invention is to provide a composition that can form a film with excellent stain resistance, as well as a film, an optical film, and an image display device.

[0007] As a result of diligent research to achieve the above objectives, the present inventors have discovered that a film with excellent antifouling properties can be formed by using a composition containing a copolymer (antifouling agent) having repeating units A derived from a hydrophobic monomer and repeating units B having a predetermined structure such as a polyalkylene oxide structure, and having a weight-average molecular weight in the range of 2,000 to 500,000. Thus, the present inventors have completed the present invention. In other words, the present inventors have found that the above objectives can be solved by the following configuration.

[0008] [1] A composition containing an antifouling agent, wherein the antifouling agent is a copolymer having repeating units A derived from a hydrophobic monomer and repeating units B having at least one structure selected from the group consisting of a polyalkylene oxide structure, a polyester structure, and a structure containing two or more monocyclic aromatic rings, and the weight-average molecular weight of the copolymer is 2,000 to 500,000. [2] The composition according to [1], wherein the weight-average molecular weight of the copolymer is 25,000 to 500,000. [3] The composition according to [1] or [2], wherein repeating unit A is at least one of the repeating units represented by formulas (2) to (4) described later. [4] The composition according to [3], wherein repeating unit A has at least two types: a repeating unit represented by formula (2) described later and a repeating unit represented by formula (3) described later. [5] The composition according to any one of [1] to [4], wherein the content of repeating unit A is 40% by mass or more with respect to the total mass of all repeating units of the copolymer. [6] The composition according to any one of [1] to [5], wherein the copolymer further comprises a repeating unit C containing a crosslinkable group. [7] The composition according to [6], wherein the crosslinkable group is at least one group selected from the group consisting of epoxy group, oxetane group, alkoxysilane group, vinyl group, styryl group, acryloyl group, methacryloyl group, and maleimide group. [8] The composition according to [6] or [7], wherein the repeating unit (C) does not contain either a hydroxyl group or a urethane bond. [9] The composition according to any one of [6] to [8], wherein the content of repeating unit A is 60 to 90% by mass, the content of repeating unit B is 5 to 35% by mass, and the content of repeating unit C is 5 to 35% by mass, based on the total mass of all repeating units of the copolymer.

[10] The composition according to any one of [1] to [9], further comprising a curable monomer.

[11] The composition according to

[10] , wherein the curable monomer is a compound having two or more acryloyl groups or methacryloyl groups.

[12] A film formed using any of the compositions described in [1] to

[11] .

[13] The film described in

[12] , which is a film obtained by curing the composition.

[14] An optical film having the film described in

[13] .

[15] An image display device having the film described in

[13] .

[0009] According to the present invention, a composition capable of forming a film with excellent antifouling properties, as well as a film, an optical film, and an image display device can be provided.

[0010] The present invention will now be described in detail. The following descriptions of constituent elements may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, numerical ranges expressed using "~" mean ranges that include the numbers written before and after "~" as lower and upper limits. In this specification, an upper or lower limit stated in a numerical range described in steps may be replaced with an upper or lower limit in another numerical range described in steps. In addition, an upper or lower limit stated in a numerical range described in this specification may be replaced with a value shown in the examples. In this specification, each component may be made using one substance alone or two or more substances in combination. Here, when two or more substances are used in combination for each component, the content for that component refers to the total content of the substances used in combination, unless otherwise specified. In this specification, the bonding direction of the divalent group (e.g., -O-CO-) is not particularly limited, for example, "L １ -L ２ -L ３ In the combination of "L ２ If L is -O-CO-, １ The position where it is joined to the side is *1, L ３ If we denote the position where it is joined to the side as *2, then L ２ *1-O-CO-*2 may also be *1-CO-O-*2.

[0011] In this specification, Re(λ) and Rth(λ) represent the in-plane retardation and thickness-direction retardation at wavelength λ, respectively. Unless otherwise specified, wavelength λ is assumed to be 550 nm. Furthermore, in this specification, Re(λ) and Rth(λ) are values ​​measured at wavelength λ using an AxoScan OPMF-1 (manufactured by OptoScience Co., Ltd.). Specifically, by inputting the average refractive index ((nx + ny + nz) / 3) and film thickness (d) into the AxoScan OPMF-1, the following can be calculated in the slow-speed axis direction (°): Re(λ) = R0(λ) Rth(λ) = ((nx + ny) / 2 - nz) × d Note that R0(λ) is displayed as a value calculated by the AxoScan OPMF-1, but it means Re(λ).

[0012] In this specification, examples of substituents (monovalent substituents) include the substituents listed in substituent group A below. In this specification, "may have substituents" includes not only embodiments without substituents but also embodiments having one or more substituents. <Substituent Group A> Substituents include, for example, halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom); alkyl groups (preferably C1 to C48, more preferably C1 to C24, particularly preferably C1 to C8 alkyl groups, for example, linear alkyl groups having C1 to C6 (e.g., methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), branched alkyl groups having C3 to C6 (e.g., isopropyl group, isobutyl group, tert-butyl group, sec-butyl group, neopentyl group, isohexyl group, 3-methylpentyl group), and cyclic alkyl groups having C3 to C12 (e.g., cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group)); Alkenyl groups (preferably 2 to 48 C12, more preferably 2 to 18 C12 alkenyl groups, for example vinyl groups, allyl groups, 1-butenyl groups, 2-butenyl groups); Alkynyl groups (preferably 2 to 6 C12 alkynyl groups, more preferably 2 to 4 C12 alkynyl groups, for example ethynyl groups, 1-propynyl groups, propargyl groups, 1-butynyl groups, 2-butynyl groups); Aryl groups (preferably 6 to 48 C12, more preferably 6 to 24 C12 aryl groups, for example phenyl groups, oligoaryl groups (naphthyl groups, anthryl groups), phenanthrenyl groups, fluorenyl groups, pyrenyl groups, triphenylenyl groups, biphenyl groups); Heteroaryl groups (preferably heterocyclic groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazole-1-yl group);Arylalkyl groups (preferably arylalkyl groups having 7 to 15 carbon atoms, for example, benzyl group, phenethyl group, methylbenzyl group, phenylpropyl group, 1-methylphenylethyl group, phenylbutyl group, 2-methylphenylpropyl group, tetrahydronaphthyl group, naphthylmethyl group, naphthylethyl group, indenyl group, fluorenyl group, anthracenylmethyl group (anthrylmethyl group), phenanthrylmethyl group (phenanthrylmethyl group)); silyl groups (preferably silyl groups having 3 to 38 carbon atoms, more preferably silyl groups having 3 to 18 carbon atoms, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group); hydroxyl groups; cyano groups; nitro groups; morpholino groups; Alkoxy groups (preferably alkoxy groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group, dodecyloxy group, cycloalkyloxy group (for example, cyclopentyloxy group, cyclohexyloxy group)); aryloxy groups (preferably aryloxy groups having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenoxy group, 1-naphthoxy group); alkenyloxy groups (preferably alkenyloxy groups having 2 to 6 carbon atoms, for example, vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, prenyloxy group); Heterocyclic oxy groups (preferably heterocyclic oxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group); silyloxy groups (preferably silyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, trimethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylmethylsilyloxy group); acyloxy groups (preferably acyloxy groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetoxy group, pivaloyloxy group, benzoyloxy group, dodecanoyloxy group, acryloyloxy group, methacryloyloxy group);Hydroxyalkylene oxy groups (preferably hydroxyalkylene oxy groups having 2 to 10 carbon atoms, for example, hydroxyethylene oxy groups); alkoxycarbonyl oxy groups (preferably alkoxycarbonyl oxy groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, ethoxycarbonyl oxy groups, t-butoxycarbonyl oxy groups, cycloalkyloxycarbonyl oxy groups (for example, cyclohexyloxycarbonyl oxy groups)); aryloxycarbonyl oxy groups (preferably aryloxycarbonyl oxy groups having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarbonyl oxy groups); carbamoyl oxy groups (preferably carbamoyl oxy groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N,N-dimethylcarbamoyl oxy groups, N-butylcarbamoyl oxy groups, N-phenylcarbamoyl oxy groups, N-ethyl-N-phenylcarbamoyl oxy groups); Sulfamoyloxy groups (preferably sulfamoyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N,N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group); Alkylsulfonyloxy groups (preferably alkylsulfonyloxy groups having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group); Arylsulfonyloxy groups (preferably arylsulfonyloxy groups having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenylsulfonyloxy group); Acyl groups (preferably acyl groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, formyl group, acetyl group, acryloyl group, methacryloyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group); Alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group);Aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarbonyl group); Carbamoyl groups (preferably carbamoyl groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, carbamoyl group, N,N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N,N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N,N-dicyclohexylcarbamoyl group); Amino groups (preferably amino groups having 32 or fewer carbon atoms, more preferably 24 or fewer carbon atoms, for example, amino group, methylamino group, N,N-dimethylamino group, N,N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexylamino group); Anilino group (preferably anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, anilino group, N-methylanilino group); heterocyclic amino group (preferably heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 4-pyridylamino group); carbonamide group (preferably carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamide group, benzamide group, tetradecaneamide group, pivaloylamide group, cyclohexaneamide group); ureido group (preferably carbonamide group having 1 to 32 carbon atoms, more preferably carbonamide group having 1 to 24 carbon atoms, for example, ureido group, N,N-dimethylureido group, N-phenylureido group); imide group (preferably imide group having 36 carbon atoms or less, more preferably carbon atoms of 24 carbon atoms or less, for example, N-succinimide group, N-phthalimide group); Alkoxycarbonylamino groups (preferably alkoxycarbonylamino groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group); aryloxycarbonylamino groups (preferably aryloxycarbonylamino groups having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarbonylamino group);Sulfonamide groups (preferably sulfonamide groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide); sulfamoylamino groups (preferably sulfamoylamino groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N,N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino); azo groups (preferably azo groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, phenylazo, 3-pyrazolylazo); alkylthio groups (preferably alkylthio groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio); Arylthio groups (preferably arylthio groups having 6 to 48 carbon atoms, more preferably arylthio groups having 6 to 24 carbon atoms, for example, phenylthio groups); heterocyclic thio groups (preferably heterocyclic thio groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 2-benzothiazolylthio groups, 2-pyridylthio groups, 1-phenyltetrazolylthio groups); alkylsulfinyl groups (preferably alkylsulfinyl groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, dodecanesulfinyl groups); arylsulfinyl groups (preferably arylsulfinyl groups having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenylsulfinyl groups); Alkylsulfonyl groups (preferably alkylsulfonyl groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group); arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example phenylsulfonyl group, 1-naphthylsulfonyl group);a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, for example, a sulfamoyl group, N,N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group); a phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group); a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a diethoxyphosphinoylamino group, dioctyloxyphosphinoylamino group); an epoxy group; -NHCOCH; ３ ; -SO ２ NHC ２ H ４ OCH ３ ; -NHSO ２ CH ３ ; and the like, and two or more of these may be combined. These substituents may be further substituted with these substituents. When two or more substituents are present, they may be the same or different from each other. Further, when possible, they may be bonded to each other to form a ring.

[0013] [Composition] The composition of the present invention is a composition containing an antifouling agent. The antifouling agent contained in the composition of the present invention is a copolymer having a repeating unit A derived from a hydrophobic monomer, and a repeating unit B comprising at least one structure selected from the group consisting of a polyalkylene oxide structure, a polyester structure, and a structure containing two or more monocyclic aromatic rings (hereinafter also referred to as "specific copolymer"). The weight average molecular weight of the specific copolymer is 2000 to 500000. The specific copolymer preferably does not contain a fluorine atom in the repeating unit A, and more preferably is a copolymer containing no fluorine atom.

[0014] As described above, in the present invention, a film with excellent antifouling properties can be formed by using a composition containing a specific copolymer. The details of this reason are not yet clear, but the inventors speculate that it is due to the following reasons. First, since the specific copolymer has repeating units A, it is thought to be unevenly distributed on the surface of the film. Here, the copolymer used in Comparative Example 1 (i.e., the water repellent corresponding to Patent Document 1), which will be described later, has repeating units A similar to those in Example 1, but does not have repeating units B, resulting in poor antifouling properties of the film. This result is thought to be because, when using the composition containing the copolymer used in Comparative Example 1, a uniform film could not be formed due to reasons such as the occurrence of repelling. Therefore, in the present invention, because the specific copolymer has repeating units B, the portion of repeating units A is more likely to face the air interface side of the film, so the occurrence of repelling is suppressed, and as a result, a uniform film is formed and the antifouling properties are improved. The specific copolymer contained in the composition of the present invention, as well as any optional components, will be described in detail below.

[0015] [Specific Copolymer] The specific copolymer (i.e., antifouling agent) contained in the composition of the present invention, as described above, has repeating units A derived from a hydrophobic monomer and repeating units B comprising at least one structure selected from the group consisting of a polyalkylene oxide structure, a polyester structure, and a structure containing two or more monocyclic aromatic rings. Furthermore, the weight-average molecular weight of the specific copolymer is 2,000 to 500,000, as described above.

[0016] In the present invention, the weight-average molecular weight of the specific copolymer is preferably 25,000 to 500,000, more preferably 25,000 to 100,000, and even more preferably 25,000 to 60,000, for the reason that the antifouling properties of the formed film are better. Here, the weight-average molecular weight in the present invention is the value measured by gel permeation chromatography (GPC) under the following conditions. • Solvent (eluent): Tetrahydrofuran • Instrument name: EcoSEC HLC-8320GPC (Tosoh Corporation) • Columns: Three columns connected together: TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (all Tosoh Corporation) • Column temperature: 40°C • Sample concentration: 0.1% by mass • Flow rate: 0.35 ml / min • Calibration curve: Calibration curve using six samples of TOSOH TSK standard polystyrene Mw = 706000 to 1013 (Mw / Mn = 1.03 to 1.06) was used.

[0017] <Repeating Unit A> The repeating unit A of the specific copolymer is a repeating unit derived from a hydrophobic monomer. Here, a hydrophobic monomer is a monomer whose CLogP value calculated by ChemDraw is greater than 4. As the hydrophobic monomer, monomers having a hydrophobic group and a polymerizable group are preferred. As the hydrophobic group, it is preferable to have an alkyl group having 1 to 50 carbon atoms or an alkenyl group having 2 to 50 carbon atoms having at least one (preferably 2 to 60, more preferably 4 to 20) silicon atoms as substituents, or an alkyl group having 4 or more carbon atoms (preferably 5 to 50, more preferably 5 to 40 carbon atoms) having two or more (preferably 3 or more, more preferably 4 to 10) terminal methyl groups. As the polymerizable group, known radical polymerizable groups and cationic polymerizable groups are preferred, and acryloyl groups or methacryloyl groups are more preferred.

[0018] In the present invention, it is preferable that the repeating unit A is at least one of the repeating units represented by the following formulas (2) to (4) for the reason that the antifouling properties of the formed film are better. Of these, it is preferable that the repeating unit A includes at least two types: the repeating unit represented by the following formula (2) and the repeating unit represented by the following formula (3) for the reason that the antifouling properties of the formed film are even better.

[0019]

[0020] In equations (2) to (4) above, m represents an integer from 2 to 16, n represents an integer from 2 to 10000, and p represents an integer from 1 to 8. １１ and R １２ Each of these independently represents either a hydrogen atom or an alkyl group. １３ L represents a hydrogen atom or substituent. １１ is -O- or -NR Ｚ Represents -. R Ｚ L represents a hydrogen atom or substituent. ２１ This represents an m+1 valent linking group. ２２ L represents a single bond or a divalent linking group. ２３ R represents a single bond or a p+1 valent linking group. ２１ ~R ２５ Each of these independently represents an alkyl group, alkenyl group, aryl group, or alkylenearyl group, which may have substituents. However, in formula (2) above, multiple R ２１ These may be the same or different, and there may be multiple R ２２ These may be the same or different, and there may be multiple R ２３ These may be the same or different. Also, in formula (3) above, multiple R ２４ These may be the same or different, and there may be multiple R ２５ These may be the same or different. X represents an alkyl group having 4 to 40 carbon atoms and having two or more terminal methyl groups. However, if p is an integer from 2 to 8, the multiple Xs may be the same or different.

[0021] - Repeating unit represented by equation (2) -

[0022] As stated above, m in formula (2) represents an integer from 2 to 16, but is preferably an integer from 3 to 15, more preferably an integer from 3 to 10, and even more preferably an integer from 3 to 6.

[0023] In the above formula (2), R １１ and R １２ As described above, each independently represents a hydrogen atom or an alkyl group. Here, examples of alkyl groups include linear alkyl groups having 1 to 18 carbon atoms, branched alkyl groups having 3 to 18 carbon atoms, or cyclic alkyl groups. Specifically, examples include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, cyclohexyl group, etc. In the present invention, R １１ and R １２ Preferably, it is a hydrogen atom.

[0024] In the above formula (2), R １３ As described above, R represents a hydrogen atom or a substituent. Here, examples of substituents include those listed in substituent group A above (particularly alkyl groups, alkenyl groups, and aryl groups). In the present invention, R １３ Preferably, the group is a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, even more preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom or a methyl group.

[0025] In the above formula (2), L １１ As mentioned above, -O- or -NR Ｚ - represents R Ｚ R represents a hydrogen atom or substituent. Ｚ Examples of substituents represented by include those listed in substituent group A above, among which alkyl groups are preferred, linear alkyl groups having 1 to 4 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred. In the present invention, L １ As for the nucleotide, -O- or -NH- is preferred, and -O- is more preferred.

[0026] In the above formula (2), L ２１ As described above, represents an m+1 valent linking group. Examples of the above m+1 valent linking group include, for example, an m+1 valent hydrocarbon group having 1 to 50 carbon atoms, which may have substituents, and in which some of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms. Examples of substituents that the above hydrocarbon group may have include those listed in substituent group A above, among which alkyl groups are preferred, linear alkyl groups having 1 to 4 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred. Examples of heteroatoms that may substitute for some of the carbon atoms include silicon atoms, oxygen atoms, and nitrogen atoms. L ２１ Examples include the groups represented by the following structural formulas K-1-L to K-6-L. In the substructure formulas, * represents L in formula (2). １１ This represents the bonding position with, and ** is -SiR in equation (2). ２１ R ２２ R ２３ This represents the bonding position with the group represented by . Of these, L ２１ The group represented by the following structural formula K-1-L is preferred.

[0027]

[0028] In the above formula (2), R ２１ ~R ２３ As described above, each independently represents an alkyl group, alkenyl group, aryl group, or alkylenearyl group, which may have substituents. However, multiple R ２１ These may be the same or different, and there may be multiple R ２２ These may be the same or different, and there may be multiple R ２３These may be the same or different. Here, examples of the alkyl group include linear alkyl groups having 1 to 18 carbon atoms, and branched or cyclic alkyl groups having 3 to 18 carbon atoms. Examples of the alkenyl group include alkenyl groups having 2 to 12 carbon atoms. Examples of the aryl group include aryl groups having 6 to 12 carbon atoms. Examples of the alkylenearyl group include alkylenearyl groups having 7 to 30 carbon atoms. Specifically, a group combining an alkylene group having 1 to 4 carbon atoms and an aryl group having 6 to 12 carbon atoms is mentioned. Furthermore, examples of substituents that the alkyl group may have include the substituents listed in substituent group A above, among which alkyl groups, alkylcarbonyl groups, alkyloxycarbonyl groups, alkylcarbonyloxy groups, or alkoxy groups are preferred. In the present invention, R ２１ ~R ２３ It is preferable that both are alkyl groups because this further improves the antifouling properties of the formed film.

[0029] - Repeating unit represented by equation (3) -

[0030] R in equation (3) above １１ , R １２ , R １３ , L １１ , R ２１ , R ２２ , and, R ２３ This is the same as that described in formula (2) above, and the preferred embodiment is also the same.

[0031] As stated above, n in formula (3) represents an integer from 2 to 10000, but is preferably an integer from 5 to 5000, more preferably from 10 to 1000, even more preferably from 12 to 500, and particularly preferably from 15 to 300.

[0032] In the above formula (3), L ２２ As mentioned above, L represents a single bond or a divalent linking group. Here, ２２One embodiment of the divalent linking group is, for example, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. The aliphatic hydrocarbon group is preferably an alkylene group having 1 to 15 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms. Furthermore, -CH₂, which constitutes part of the aliphatic hydrocarbon group, is also included. ２ One or more of these groups may be independently substituted with groups selected from -O-, -S-, -CO-, and -N(Q)-. Note that substitutions with these groups are permitted for two or more -CH groups, as long as no adjacent groups are substituted with the same group. ２ You may substitute -. That is, for example, -CH ２ -CH ２ The - may be substituted with -O-CO-, but it cannot be substituted with -O-O-. Q represents a hydrogen atom or substituent. L ２２ Preferably, the alkylene group has 2 to 8 carbon atoms, which may have substituents.

[0033] Also, L ２２ Regarding the divalent linking group represented by one aspect of Q, substituents that may be present include divalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and substituents represented by one aspect of Q include those listed in the substituent group A above, among which, for example, are hydroxyl groups, halogen atoms, amino groups, alkyl groups, alkoxy groups, acyl groups, aryl groups, nitro groups, cyano groups, alkylcarbonyl groups, and sulfonyl groups.

[0034] R in equation (3) above ２４ and R ２５ As described above, each independently represents an alkyl group, alkenyl group, aryl group, or alkylenearyl group, which may have substituents. Specific examples of these are shown in formula (2) above, R ２１ ~R ２３ Examples of those described in [reference] are given. In the present invention, R ２４ and R ２５ It is preferable that the element be an alkyl group because it provides even better antifouling properties to the resulting film.

[0035] - Repeating unit represented by equation (4) -

[0036] In the above formula (4), R １１ , R １２ , R １３ , and, L １１ This is the same as that described in formula (2) above, and the preferred embodiment is also the same.

[0037] As mentioned above, p in formula (4) represents an integer from 1 to 8, but is preferably an integer from 1 to 5, and more preferably an integer from 1 to 4.

[0038] In the above formula (4), L ２３ As described above, represents a single bond or a p+1 valent linking group. Examples of the p+1 valent linking group include, for example, a p+1 valent hydrocarbon group having 1 to 50 carbon atoms, which may have substituents, and in which some of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms. Examples of substituents that the hydrocarbon group may have include those listed in substituent group A above, among which alkyl groups are preferred, linear alkyl groups having 1 to 4 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred. Examples of heteroatoms that may substitute for some of the carbon atoms include silicon atoms, oxygen atoms, and nitrogen atoms. ２３ Examples include the groups represented by the following structural formulas K-7-L to K-9-L. In the substructure formulas, * represents L in formula (3). １１ This represents the bonding position with, and ** represents the bonding position with X in formula (3). In the present invention, L ２３ Preferably, the group consists of a single bond or a group represented by the following structural formula K-8-L.

[0039]

[0040] As described above, X in formula (4) represents an alkyl group having 4 to 40 carbon atoms and having two or more terminal methyl groups. However, if p is an integer from 2 to 8, the multiple Xs may be the same or different. Here, "terminal methyl group" means a methyl group that constitutes the end of a linear or side chain of a hydrocarbon group. For example, linear alkyl groups such as n-propyl and n-butyl groups are alkyl groups having one terminal methyl group, isopropyl groups are alkyl groups having two terminal methyl groups, and t-butyl groups are alkyl groups having three terminal methyl groups. For example, n-hexyl groups have 6 carbon atoms and are alkyl groups having one terminal methyl group, but any of the groups represented by formulas (a-1) to (a-3) below all have 4 to 40 carbon atoms and have two or more terminal methyl groups (methyl groups enclosed by dotted lines in the formulas below). The number of terminal methyl groups is two or more, preferably three or more, and more preferably four to ten.

[0041]

[0042] Specific examples of repeating unit A include the repeating units represented by the following formulas K-1 to K-26. In the repeating units exemplified below, n represents an integer from 2 to 10000.

[0043] The repeating unit A may be used alone, or two or more types may be used in combination. In the present invention, the content of the repeating unit A is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably more than 60% by mass, based on the total mass of all repeating units of the specific copolymer, for the reason that the antifouling property of the formed film becomes more favorable. In addition, the upper limit of the content of the repeating unit A is preferably 90% by mass or less, and more preferably 85% by mass or less. Furthermore, when the repeating unit A has two types, the repeating unit represented by the above formula (2) (hereinafter abbreviated as "A2" in this paragraph) and the repeating unit represented by the above formula (3) (hereinafter abbreviated as "A3" in this paragraph), the mass ratio of A2 and A3 is preferably A2:A3 = 1:10 to 10:1, and more preferably 1:5 to 5:1.

[0044] <Repeating Unit B> The repeating unit B contained in the specific copolymer is a repeating unit comprising at least one structure selected from the group consisting of a polyalkylene oxide structure, a polyester structure, and a structure containing two or more monocyclic aromatic rings.

[0045] -Repeating Unit Having Polyalkylene Oxide Structure- Preferable examples of the repeating unit having a polyalkylene oxide structure include the repeating unit represented by the following formula (1-1).

[0046]

[0047] In the above formula (1-1), R １１ and R １２ each independently represent a hydrogen atom or an alkyl group. R １３ represents a hydrogen atom or a substituent. L １１ represents -O- or -NR Ｚ -. R Ｚ represents a hydrogen atom or a substituent. L ２４represents a single bond or a divalent linking group. A represents an alkylene group, provided that a plurality of A's may be the same as or different from each other. q represents an integer of 2 or more. R ２６ represents a hydrogen atom or a substituent.

[0048] In the above formula (1-1), R １１ , R １２ , R １３ , and L １１ are the same as those described in the above formula (2), and preferred embodiments thereof are also the same.

[0049] In the above formula (1-1), L ２４ represents a single bond or a divalent linking group as described above. Here, the divalent linking group represented by one aspect of L ２４ is the same as those described in the above formula (3), and preferred embodiments thereof are also the same. In the present invention, L ２４ is preferably a single bond.

[0050] As described above, A in the above formula (1-1) represents an alkylene group, provided that a plurality of A's may be the same as or different from each other. Here, the number of carbon atoms in the alkylene group represented by A is preferably 1 to 4, more preferably 2 to 4. For example, when A is an alkylene group having 1 carbon atom, -A-O- in the above formula (1-1) represents an oxymethylene group (-CH ２ O-), and when A is an alkylene group having 2 carbon atoms, -A-O- in the above formula (1-1) represents an oxyethylene group (-CH ２ CH ２ O-). The alkylene group may be either linear or branched. For example, when A is a branched alkylene group having 3 carbon atoms, -A-O- in the above formula (1-1) represents an oxy(methylethylene) group [-CH ２ CH(CH ３ )O-], and when A is a branched alkylene group having 4 carbon atoms, -A-O- in the above formula (1-1) represents an oxy(ethylethylene) group [-CH ２ CH(CH ２ CH ３ )O-].

[0051] In the above formula (1-1), -(A-O)q- may be an oxyalkylene group formed by linking two or more different oxyalkylene groups. The bonding order of the linked oxyalkylene groups may be random or block-type. For example, it may be an oxyalkylene group formed by linking an oxyethylene group and an oxy(methylethylene) group, or it may be an oxyalkylene group formed by linking an oxy(methylethylene) group and an oxy(ethylethylene) group.

[0052] As mentioned above, q in formula (1-1) represents an integer of 2 or more, but is preferably an integer between 2 and 1000, and more preferably an integer between 2 and 25.

[0053] In the above formula (1-1), R ２６ As described above, R represents a hydrogen atom or a substituent. Here, examples of substituents include those listed in substituent group A above (particularly alkyl groups, alkenyl groups, and aryl groups). In the present invention, R ２６ Preferably, the group is a hydrogen atom, an alkyl group, or a phenyl group; more preferably, a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms; even more preferably, a hydrogen atom, a methyl group, or an ethyl group; and particularly preferably, a hydrogen atom or a methyl group.

[0054] Examples of repeating units having a polyalkylene oxide structure include the repeating units represented by the following formulas H-1 to H-13. In the repeating units exemplified below, q, r, and s each independently represent an integer of 2 or more.

[0055] - Repeating units having a polyester structure - Examples of repeating units having a polyester structure include repeating units represented by the following formula (1-2).

[0056]

[0057] In the above formula (1-2), R １１ and R １２ Each of these independently represents either a hydrogen atom or an alkyl group. １３L represents a hydrogen atom or substituent. １１ is -O- or -NR Ｚ Represents -. R Ｚ L represents a hydrogen atom or substituent. ２５ R represents a divalent aliphatic hydrocarbon group containing two or more ester bonds. As mentioned above, the orientation of the ester bonds is not limited and may be either -O-CO- or -CO-O-. ２７ represents a hydrogen atom or substituent.

[0058] In the above equation (1-2), R １１ , R １２ , R １３ , and, L １１ This is the same as that described in formula (2) above, and the preferred embodiment is also the same.

[0059] In the above formula (1-2), L ２５ As mentioned above, this represents a divalent aliphatic hydrocarbon group containing two or more ester bonds. Examples of such divalent aliphatic hydrocarbon groups include -CH, which constitutes part of an alkylene group. ２ Examples include alkylene groups that form two or more ester bonds by being substituted with -O- and -CO-, and specifically, the following linking groups are preferred. Note that * １ L in the above formula (1-2) is １１ This indicates the connection position with * ２ This is R in the above equation (1-2). ２７ This indicates the connection point with [the other element]. １ -L-NH-CO-(OL-CO-OL-CO)t-OL-NH-CO-* ２ * １ -L-O-(CO-L-O)t-* ２ * １ -L-O-(CO-L-O)t-CO-NH-* ２ Here, t represents an integer of 2 or more, preferably an integer between 2 and 1000, and more preferably an integer between 2 and 25. L represents an alkylene group having 1 to 12 carbon atoms, which may have substituents, and preferably an alkylene group having 1 to 6 carbon atoms, which may have substituents. Note that multiple Ls may be the same or different.

[0060] In the above equation (1-2), R ２７ As described above, R represents a hydrogen atom or a substituent. Here, examples of substituents include those listed in substituent group A above (particularly alkyl groups, alkenyl groups, and aryl groups). In the present invention, R ２７ Preferred elements include hydrogen atoms, alkyl groups, or phenyl groups.

[0061] Examples of repeating units having a polyester structure include the repeating units represented by the following formulas H-14 to H-16. In the repeating units exemplified below, t represents an integer of 2 or more.

[0062] - Repeating Units Having a Structure Containing Two or More Monocyclic Aromatic Rings - Repeating units having a structure containing two or more monocyclic aromatic rings will be described. Here, a monocyclic aromatic ring refers to an unfused monocyclic aromatic ring or an individual monocyclic aromatic ring within a fused ring. That is, a phenyl group is a group having one benzene ring, which is a monocyclic aromatic ring, and a naphthyl group is a group having two benzene rings, which are monocyclic aromatic rings. Furthermore, the number of atoms constituting the ring of a monocyclic aromatic ring is not particularly limited, but it is sufficient to be around 5 to 18, preferably 5 to 10, and more preferably 5 to 6. Furthermore, the monocyclic aromatic ring may be an aromatic ring consisting only of carbon, or it may be a heterocyclic aromatic ring containing elements other than carbon in its ring structure. An example of an aromatic ring is a benzene ring. An example of a heterocyclic aromatic ring is an aromatic ring containing one or more atoms selected from sulfur atoms, nitrogen atoms, and oxygen atoms. The heteroaromatic ring is preferably one containing a sulfur atom, and more preferably one containing one sulfur atom. Specific examples of heteroaromatic rings include thiophene rings, pyrrole rings, imidazole rings, pyrazole rings, furan rings, isothiazole rings, isoxazole rings, pyridine rings, pyrazine rings, and pyrimidine rings. The monocyclicaromatic rings are preferably benzene rings, thiophene rings, and pyridine rings, and more preferably benzene rings.

[0063] The repeating unit having a structure containing two or more monocyclic aromatic rings is preferably a repeating unit containing a structure represented by the following formula (B-1).

[0064]

[0065] In the above formula (B-1), * represents the bond position. Also, R ２１ and R ２２ Each of these independently represents a hydrogen atom or an alkyl group. Also, R ２３ L represents a hydrogen atom or substituent. １ is -O- or -NR Ｚ It represents -. However, R Ｚ represents a hydrogen atom or substituent.

[0066] Here, R ２１ and R ２２ Examples of alkyl groups represented by one embodiment include linear alkyl groups having 1 to 18 carbon atoms, branched alkyl groups having 3 to 18 carbon atoms, or cyclic alkyl groups. Specifically, examples include methyl groups, ethyl groups, propyl groups, butyl groups, isopropyl groups, tert-butyl groups, and cyclohexyl groups. ２１ and R ２２ Preferably, it is a hydrogen atom. Also, R ２３ Examples of substituents shown in one aspect include the substituents listed in the substituent group A above (particularly alkyl groups, alkenyl groups, and aryl groups). ２３ As for the group, a hydrogen atom or an alkyl group is preferred, a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms is more preferred, a hydrogen atom, a methyl group, or an ethyl group is even more preferred, and a hydrogen atom or a methyl group is particularly preferred. Also, L １ One aspect of this is shown - NR Ｚ Regarding R Ｚ The substituent shown in one embodiment is preferably an alkyl group, more preferably a linear alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or an ethyl group. １ Preferably, it is -O- or -NH-, and more preferably -O-.

[0067] In the present invention, it is preferable that the repeating unit having a structure containing two or more monocyclic aromatic rings is a repeating unit represented by any of the following formulas (b1) to (b3).

[0068]

[0069] In the above formulas (b1) to (b3), R ２１ , R ２２ and R ２３ and L １ This is the same as what was explained in formula (B-1) above. Also, in formula (b3) above, R ２４ and R ２５ Each of these independently corresponds to R in the above formula (B-1). ２１ and R ２２ The definition is the same as for the preferred embodiment. ２６ R in the above formula (B-1) is ２３ The definition is the same as for the preferred embodiment. ２ L in the above formula (B-1) １ The definition is the same as, and the preferred embodiment is also the same. Also, SP １ and SP ２ Each of these independently represents a spacer group. Also, Ph １ This represents a ring structure containing two or more monocyclic aromatic rings. Also, M １ represents a mesogenic group. Also, T １ This represents a terminal group.

[0070] In the above formulas (b1) to (b3), SP １ and SP ２ Specific examples of the spacer group represented by include divalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms. Here, as the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, for example, alkylene groups having 1 to 15 carbon atoms are preferred, and alkylene groups having 1 to 8 carbon atoms are more preferred. Also, -CH, which constitutes part of the divalent hydrocarbon group, is also included. ２ - of which one or two or more non-adjacent -CH ２Each of these may be independently substituted with -O-, -S-, -NH-, or -N(Q)-. The substituent represented by Q is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. The spacer group is *-[(CH ２ ) ｎ１ O] ｍ１ It is preferable that the base is represented by -*. Here, m1 is an integer from 1 to 4, n1 is an integer from 2 to 4, and * is L １ or Ph １ (M １ This indicates the connection position with ).

[0071] In the above formula (b1), Ph １ Examples of ring structures containing two or more monocyclic aromatic rings represented by include naphthyl groups and biphenyl groups, which may have substituents, with naphthyl groups being preferred. The substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or an ethyl group.

[0072] In the above formulas (b2) and (b3), M １The mesogenic group represented by is a group that represents the main skeleton of a liquid crystal molecule that contributes to liquid crystal formation. Liquid crystal molecules exhibit liquid crystalline properties, which is an intermediate state (mesophase) between the crystalline state and the isotropic liquid state. There are no particular restrictions on the mesogenic group; for example, refer to the description on pages 7 to 16 of "Flussigé Kristalle in Tabellen II" (VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, 1984) and the description on Chapter 3 of the Liquid Crystal Handbook (Maruzen, 2000), edited by the Liquid Crystal Handbook Editorial Committee. As the mesogenic group, for example, a group having at least one cyclic structure selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups is preferred. The mesogenic group is preferably a group having an aromatic hydrocarbon group or an alicyclic group, which may have substituents, more preferably a group having 2 to 4 aromatic hydrocarbon groups, and even more preferably a group having 3 aromatic hydrocarbon groups. The substituents are preferably alkyl groups, alkoxy groups, alkyl ester groups, and acetyl groups, and more preferably methyl groups, tert-butyl groups, methoxy groups, and methyl ester groups.

[0073] Furthermore, M in the above formulas (b2) and (b3) １ Preferably, represents a mesogenic group represented by the following formula (M1-A).

[0074]

[0075] In the above formula (M1-A), * represents SP １ or T １ (or SP) 2 This represents the connection position with ). Also, n represents an integer of 1 or more, preferably an integer between 1 and 10. １１ and Ph １２ Each of these independently represents a divalent aromatic ring group which may have substituents. However, when n represents an integer of 2 or more, multiple Ph １１ These may be the same or different. Also, L １１represents a single bond or a divalent linking group. However, if n is an integer of 2 or more, multiple L １１ These may be the same or different.

[0076] Ph １１ and Ph １２ The divalent aromatic ring group represented by can be a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring, or a group obtained by removing two hydrogen atoms from an aromatic heterocycle. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, and phenanthroline rings. Examples of aromatic heterocycles include furan rings, pyrrole rings, thiophene rings, pyridine rings, thiazole rings, and benzothiazole rings. Among these, a group obtained by removing two hydrogen atoms from a benzene ring (for example, a 1,4-phenyl group) is preferred. Substituents that the divalent aromatic ring group may have are preferably alkyl ester groups, alkyl groups, and acetyl groups, more preferably methyl ester groups and linear alkyl groups having 1 to 4 carbon atoms, and even more preferably methyl or ethyl groups.

[0077] L １１ Examples of divalent linking groups represented by include -CO-, -O-, -S-, -C(=S)-, and -CR. １ R ２ -, -CR ３ =CR ４ -, -NR ５ -, or a combination of two or more of these. Note that R １ ~R ５ Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

[0078] In the above formula (b2), T １The term "terminal group" refers to a hydrogen atom or a group located at the terminal end of the side chain relative to the mesogenic group. Examples of groups located at the terminal end of the side chain relative to the mesogenic group include halogen atoms, cyano groups, nitro groups, hydroxyl groups, C1-C10 alkyl groups, C1-C10 alkoxy groups, C1-C10 alkylthio groups, C1-C10 alkoxycarbonyloxy groups, C1-C10 alkoxycarbonyl groups (ROC(O)-: R is an alkyl group), C1-C10 acyloxy groups, C1-C10 acylamino groups, C1-C10 alkoxycarbonylamino groups, C1-C10 sulfonylamino groups, C1-C10 sulfamoyl groups, C1-C10 carbamoyl groups, C1-C10 sulfinyl groups, C3-C12 trialkylsilyloxy groups, and C1-C10 ureido groups. Here, -CH, which constitutes part of the alkyl group ２ - of which one or two or more non-adjacent -CH ２ Each of these substituents may be independently substituted with -O-, -S-, -NH-, or -N(Q)-. The substituent represented by Q is preferably an alkyl group having 1 to 4 carbon atoms.

[0079] Examples of repeating units having a structure containing two or more monocyclic aromatic rings include repeating units represented by the following formulas H-17 to H-37.

[0080] Repeating unit B may be used alone or in combination of two or more types. In the present invention, for the reason that the antifouling properties of the formed film are better, the content of repeating unit B is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 9% by mass or more, based on the total mass of all repeating units of the specific copolymer. Furthermore, the upper limit of the content of repeating unit B is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.

[0081] <Repeating Unit C> The specific copolymer preferably has a repeating unit C containing a crosslinkable group, for the reason that the antifouling properties and slipperiness of the formed film are improved. Here, the crosslinkable group is at least one group selected from the group consisting of epoxy group, oxetane group, alkoxysilane group, vinyl group, styryl group, acryloyl group, methacryloyl group, and maleimide group. Among these, epoxy group, acryloyl group, or methacryloyl group is preferred, and acryloyl group or methacryloyl group is more preferred.

[0082] In the present invention, it is preferable that the repeating unit (C) does not contain either a hydroxyl group or a urethane bond, in order to obtain better antifouling properties of the formed film.

[0083] As the repeating unit C mentioned above, a repeating unit represented by the following formula (5) is preferred.

[0084]

[0085] In the above formula (5), R １１ and R １２ Each of these independently represents either a hydrogen atom or an alkyl group. １３ L represents a hydrogen atom or substituent. １１ is -O- or -NR Ｚ Represents -. R Ｚ L represents a hydrogen atom or substituent. ２６ represents a single bond or a divalent linking group. P represents a crosslinking group. Examples of crosslinking groups are the same as those described above.

[0086] In the above formula (5), R １１ , R １２ , R １３ , and, L １１ This is the same as that described in formula (2) above, and the preferred embodiment is also the same.

[0087] In the above formula (5), L ２６ As mentioned above, L represents a single bond or a divalent linking group. Here, ２６The divalent linking group represented by one embodiment is the same as that described in formula (3) above, and the preferred embodiment is also the same.

[0088] Examples of repeating units C include the repeating units represented by the following formulas L-1 to L-18.

[0089] The repeating unit C may be used alone or in combination of two or more types. In the present invention, for the reason that the antifouling properties of the formed film are better, the content of the repeating unit C is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 9% by mass or more, based on the total mass of all repeating units of the specific copolymer. Furthermore, the upper limit of the content of the repeating unit B is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.

[0090] Furthermore, in the present invention, for the reason that the antifouling properties of the formed film are better, it is preferable that the content of repeating unit A is 60 to 90% by mass, the content of repeating unit B is 5 to 35% by mass, and the content of repeating unit C is 5 to 35% by mass, based on the total mass of all repeating units of the specific copolymer.

[0091] [Curable Monomers] From the viewpoint of wear resistance, the compositions of the present invention preferably further contain curable monomers. Here, curable monomers refer to polymerizable monomers having polymerizable groups, and include monofunctional polymerizable monomers and polyfunctional polymerizable monomers. Furthermore, polymerizable groups that can be radically polymerized or cationically polymerized are preferred. As radical polymerizable groups, known radical polymerizable groups can be used, and suitable examples include acryloyl groups or methacryloyl groups. As cationic polymerizable groups, known cationic polymerizable groups can be used, and specifically, examples include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, and vinyloxy groups.

[0092] The curable monomer is preferably a compound having two or more acryloyl groups or methacryloyl groups.

[0093] Examples of such curable monomers include, specifically, hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), polyethylene glycol diacrylate, polypropylene glycol diacrylate, nonanediol diacrylate, decanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol-modified bisphenol A diacrylate, dioxane glycol diacrylate, cyclohexanedimethanol diacrylate, tricyclodecanedimethanol diacrylate, and trimethylol diacrylate. Examples include methylpropane triacrylate, trimethylolpropane ethoxytriacrylate, glycerin propoxytriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol alkoxytetraacrylate, pentaerythritol ethoxytetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, polytetramethylene glycol diacrylate, tris-(2-acryloxyethyl) isocyanurate, and polyfunctional urethane acrylate.

[0094] The curable monomer may be used alone or in combination of two or more types. When the composition of the present invention contains a curable monomer, the content of the curable monomer is preferably 1 to 10,000 parts by mass, and more preferably 100 to 2,000 parts by mass, per 1 part by mass of the specific copolymer.

[0095] [Solvent] The composition of the present invention preferably contains a solvent. Examples of solvents include ketones [e.g., acetone, 2-butanone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, cyclopentanone (CPO), etc.], ethers [e.g., dioxane, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate (PGMEA), etc.], aliphatic hydrocarbons [e.g., hexane, etc.], alicyclic hydrocarbons [e.g., cyclohexane, etc.], aromatic hydrocarbons [e.g., toluene, xylene, trimethylbenzene, etc.], and halogenated carbons [e.g., di Examples of solvents include chloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc., esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (e.g., methanol (MeOH), ethanol, isopropyl alcohol (IPA), butanol, cyclohexanol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), and amides (e.g., dimethylformamide, dimethylacetamide, etc.). These solvents may be used individually or in combination of two or more.

[0096] [Polymerization Initiator] The composition of the present invention preferably contains a polymerization initiator. Preferably, the polymerization initiator is a photopolymerization initiator that can initiate the polymerization reaction by ultraviolet irradiation. Examples of photopolymerization initiators include α-carbonyl compounds, acyloin ethers, α-hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds, combinations of triarylimidazole dimers and p-aminophenyl ketones, acridine and phenazine compounds and oxadiazole compounds, acylphosphine oxide compounds, and the like. Oxime-type polymerization initiators are also preferred. Specific examples include, for example, the initiators described in paragraphs

[0049] to

[0052] of International Publication No. 2017 / 170443.

[0097] [Other Components] The composition of the present invention may contain other components besides those described above. Examples of other components include tilt angle control agents, plasticizers, and crosslinking agents. Furthermore, since the composition of the present invention can impart antifouling properties to functional layers (e.g., hard coat layers, protective layers, etc.), it may also contain main components that form functional layers (e.g., resins, rubbers, etc.). It is preferable that the liquid crystal compound content of the composition of the present invention is less than 30% by mass, more preferably less than 10% by mass, even more preferably less than 1% by mass, and particularly preferably substantially absent, based on the mass of the total solid content of the composition.

[0098] [Membrane] The membrane of the present invention is a membrane formed using the composition of the present invention described above. Preferably, the membrane of the present invention is a membrane obtained by curing the composition of the present invention described above (hereinafter also referred to as the "cured membrane of the present invention").

[0099] The method for forming the film of the present invention is not particularly limited, but one example is to apply the composition of the present invention onto a substrate and dry it. Here, known methods such as the drop method (drop casting method), spray method, and spin coating method can be used as the method for applying the composition. Furthermore, the drying temperature is preferably 50 to 150°C, and more preferably 80 to 120°C, from the viewpoint of removing any solvent contained in the composition of the present invention.

[0100] Furthermore, the method for forming the cured film of the present invention is not particularly limited, but one method involves applying the composition of the present invention onto a substrate, drying it, and then performing polymerization by light irradiation. The irradiation dose is 10 mJ / cm². ２ ~50 J / cm ２ Preferably, 20 mJ / cm ２ ~5J / cm ２ More preferably, 30 mJ / cm ２ ~3J / cm ２ More preferably, 50 to 1000 mJ / cm ２ This is particularly preferable. Furthermore, the polymerization reaction may be carried out under heating conditions to accelerate it.

[0101] The thickness of the film and cured film of the present invention is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

[0102] [Optical Film] The optical film of the present invention is an optical film having the cured film of the present invention.

[0103] [Substrate] The optical film of the present invention may have a substrate for supporting the cured film of the present invention. Such a substrate is preferably transparent. In this invention, "transparent" means that the transmittance of visible light is 60% or more, preferably 80% or more, and more preferably 90% or more.

[0104] Examples of the above-mentioned substrates include glass substrates and polymer films. Examples of polymer film materials include cellulose polymers; acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; thermoplastic norbornene polymers; polycarbonate polymers; polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin); polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymer; vinyl chloride polymers; amide polymers such as nylon and aromatic polyamides; imide polymers; sulfone polymers; polyethersulfone polymers; polyetheretherketone polymers; polyphenylene sulfide polymers; vinylidene chloride polymers; vinyl alcohol polymers; vinyl butyral polymers; arylate polymers; polyoxymethylene polymers; epoxy polymers; and polymers obtained by mixing these polymers. The thickness of the above-mentioned substrate is not particularly limited, but is preferably 1 to 200 μm, and more preferably 2 to 100 μm. The substrate is preferably peelable.

[0105] [Image Display Device] The image display device of the present invention is an image display device having the film of the present invention. The display elements used in the image display device are not particularly limited and include, for example, liquid crystal cells, organic electroluminescence (hereinafter abbreviated as "EL (Electro Luminescence)") display panels, and plasma display panels.

[0106] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0107] [Synthesis of Copolymers] Copolymers B-1 to B-8 and B-13 having repeating units A to C of the types shown in Table 1 below were synthesized. The structure of each repeating unit, indicated by type in Table 1 below, is the same as that of the specific example illustrated above. Similarly, copolymers B-9 to B-12, B-14 to B-16 and C-1 having repeating units A to C of the types shown in Table 1 below were synthesized. The weight-average molecular weights of copolymers B-1 to B-16 and C-1 are shown in Table 1 below.

[0108] [Examples 1-20 and Comparative Example 1] Copolymers B-1 to B-16 and C-1 were each diluted to 0.5% by mass with methyl isobutyl ketone, and a polymerization initiator (Omnirad 184, manufactured by BASF) at a concentration of 3% by mass relative to the mass of each copolymer was added to prepare the composition.

[0109] [Evaluation] [Preparation of evaluation samples] The prepared composition was coated onto a PET sheet with a film thickness of 100 μm with a clearance of 50 μm. The resulting film was irradiated with ultraviolet light using a metal halide lamp (manufactured by I-Graphics Co., Ltd.) at 75°C under a nitrogen atmosphere (oxygen concentration 100 vol ppm) (irradiation dose: 500 mJ / cm²). ２ ), prepare evaluation samples.

[0110] [Repulsion] When preparing evaluation samples, the coating surface is visually inspected and evaluated for repulsion according to the following evaluation criteria. The results are shown in Table 1 below. <Evaluation Criteria> A: No repulsion is observed. B: Some repulsion is observed. E: Repulsion is observed across the entire surface.

[0111] [Fouling Resistance] Generally, the lower the surface energy, the better the fouling resistance. Therefore, fouling resistance is evaluated by measuring the surface energy. Specifically, the contact angle of the evaluation sample prepared above is measured with water and diiodomethane using a contact angle meter DMo-702 manufactured by Kyowa Interface Chemical Co., Ltd. The contact angle 10 seconds after application is measured five times, and the average value is calculated. From the obtained contact angles of water and diiodomethane, the surface energy is calculated using the Owens and Wendt formula and evaluated according to the evaluation criteria below. The results are shown in Table 1 below. <Evaluation Criteria> A: Surface energy less than 17 mN / m B: Surface energy 17 mN / m or more and less than 20 mN / m C: Surface energy 20 mN / m or more and less than 25 mN / m D: Surface energy 25 mN / m or more and less than 35 mN / m E: Surface energy 35 mN / m or more

[0112] [Slipperiness] When a SUS (Steel Use Stainless) ball is rolled while a 100g load is applied to the prepared evaluation sample, the load is measured, the coefficient of dynamic friction is measured, and it is evaluated according to the following criteria. The results are shown in Table 1 below. Note that a lower coefficient of dynamic friction indicates better slipperiness. <Evaluation Criteria> A: Coefficient of dynamic friction is less than 0.10 B: Coefficient of dynamic friction is 0.10 or more and less than 0.20 C: Coefficient of dynamic friction is 0.20 or more and less than 0.30 D: Coefficient of dynamic friction is 0.30 or more and less than 0.40 E: Coefficient of dynamic friction is 0.40 or more

[0113]

[0114] The results shown in Table 1 show that when a copolymer without repeating unit B is used, repulsion occurs, resulting in poor antifouling and slipperiness of the resulting film (Comparative Example 1). In contrast, when a specific copolymer having repeating units A and B and a weight-average molecular weight of 2,000 to 500,000 is used, repulsion is suppressed, and the resulting film exhibits good antifouling and slipperiness (Examples 1 to 20). In particular, a comparison between Example 1 and Example 2 shows that when the weight-average molecular weight of the specific copolymer is 25,000 to 500,000, the antifouling properties of the formed film are even better. Furthermore, a comparison between Example 1 and Example 3 shows that when the specific copolymer has repeating unit C, the antifouling properties and slipperiness of the formed film are even better. Finally, a comparison between Example 3 and Example 6 shows that when repeating unit A consists of two types, the repeating unit represented by formula (2) and the repeating unit represented by formula (3), the antifouling properties of the formed film are even better. Furthermore, a comparison of Examples 3, 11, and 12 shows that if the repeating unit C contains neither a hydroxyl group nor a urethane bond, the antifouling properties of the formed film are improved. A comparison of Example 3 and Example 13 shows that if the content of repeating unit A is more than 60% by mass relative to the total mass of all repeating units of the specific copolymer, the antifouling properties of the formed film are improved. A comparison of Examples 13 to 16 shows that if the content of repeating unit A is 40% by mass or more relative to the total mass of all repeating units of the specific copolymer, the antifouling properties of the formed film are improved.

[0115] [Example 21] A composition with the following composition was prepared. ------------------------------------------------------------------- Composition ----------------------------------------------------------------------------------- ・0.5 parts by mass of the above copolymer B-1 ・0.5 parts by mass of the above copolymer B-2 ・0.5 parts by mass of the above copolymer C-1 ・100 parts by mass of dipentaerythritol hexaacrylate (trade name: DPHA, manufactured by Daicel Ornex) ・3 parts by mass of polymerization initiator (Omnirad 184, manufactured by BASF) ・100 parts by mass of methyl isobutyl ketone -----------------------------------------------------------------------------------

[0116] Using the prepared composition, evaluation samples were made in the same manner as in Example 1, and the repellency, stain resistance, and slipperiness were evaluated in the same manner as in Example 1. All evaluation results were favorable.

Claims

1. A composition containing an antifouling agent, wherein the antifouling agent is a copolymer having repeating units A derived from a hydrophobic monomer and repeating units B comprising at least one structure selected from the group consisting of a polyalkylene oxide structure, a polyester structure, and a structure containing two or more monocyclic aromatic rings, and the weight-average molecular weight of the copolymer is 2,000 to 500,000.

2. The composition according to claim 1, wherein the weight-average molecular weight of the copolymer is 25,000 to 500,000.

3. The composition according to claim 1, wherein the repeating unit A is at least one of the repeating units represented by the following formulas (2) to (4). Here, in the above formulas (2) to (4), m represents an integer of 2 to 16, n represents an integer of 2 to 10000, and p represents an integer of 1 to 8. R １１ and R １２ each independently represent a hydrogen atom or an alkyl group. R １３ represents a hydrogen atom or a substituent. L １１ represents -O-, or -NR Ｚ -. R Ｚ represents a hydrogen atom or a substituent. L ２１ represents an m+1 valent linking group. L ２２ represents a single bond or a divalent linking group. L ２３ represents a single bond or a p+1 valent linking group. R ２１ to R ２５ each independently represent an alkyl group, alkenyl group, aryl group, or alkylenearyl group, which may have a substituent. Provided that in the above formula (2), a plurality of R ２１ may be the same or different from each other, a plurality of R ２２ may be the same or different from each other, and a plurality of R ２３ may be the same or different from each other. Also, in the above formula (3), a plurality of R ２４ may be the same or different from each other, and a plurality of R ２５ may be the same or different from each other. X represents an alkyl group having 4 to 40 carbon atoms and having 2 or more terminal methyl groups. Provided that when p is an integer of 2 to 8, a plurality of X may be the same or different from each other.

4. The composition according to claim 3, wherein the repeating unit A comprises at least two types: a repeating unit represented by formula (2) and a repeating unit represented by formula (3).

5. The composition according to claim 1, wherein the content of the repeating unit A is 40% by mass or more with respect to the total mass of all repeating units of the copolymer.

6. The composition according to claim 1, wherein the copolymer further has repeating units C containing crosslinkable groups.

7. The composition according to claim 6, wherein the crosslinkable group is at least one group selected from the group consisting of epoxy group, oxetane group, alkoxysilane group, vinyl group, styryl group, acryloyl group, methacryloyl group, and maleimide group.

8. The composition according to claim 6, wherein the repeating unit (C) does not contain either a hydroxyl group or a urethane bond.

9. The composition according to claim 6, wherein the content of repeating unit A is 60 to 90% by mass, the content of repeating unit B is 5 to 35% by mass, and the content of repeating unit C is 5 to 35% by mass, based on the total mass of all repeating units of the copolymer.

10. The composition according to claim 1, further comprising a curable monomer.

11. The composition according to claim 10, wherein the curable monomer is a compound having two or more acryloyl groups or methacryloyl groups.

12. A film formed using the composition described in any one of claims 1 to 11.

13. The film according to claim 12, which is a film obtained by curing the composition.

14. An optical film having the film described in claim 13.

15. An image display device having the film described in claim 13.

Images