Copolymer, water and oil repellent agent, and article

Abstract

This copolymer comprises the following as monomer components: (I) a fluorine-containing monomer which has a monovalent fluoropolyether group and a polymerizable group at a terminal thereof and in which the fluoropolyether group and the polymerizable group are bonded directly or via a linker; and (II) a monomer which has at least one polymerizable group and has a molecular weight smaller than that of the fluorine-containing monomer (I). The copolymer has excellent reproducibility of the degree of polymerization and heat resistance (in particular, heat resistance of a coating film (suppression of the occurrence of cissing due to heat)). A water and oil repellent agent containing the copolymer exhibits good water and oil repellency not only initially but also under high-temperature conditions, and can maintain a uniform coating film.

Description

Copolymers, water-repellent and oil-repellent agents, and articles

[0001] The present invention relates to a copolymer having a fluorine-containing monomer as a monomer component, which exhibits excellent reproducibility of the degree of polymerization and heat resistance (particularly the heat resistance of the coating film (suppression of heat-induced repulsion)), a water-repellent and oil-repellent agent containing the copolymer, and an article having a film of the water-repellent and oil-repellent agent on its surface.

[0002] Conventionally, polymers of fluorinated acrylics or methacrylic monomers, as shown in Patent Document 1 (Japanese Patent Publication No. 1-42983) and Patent Document 2 (Japanese Patent Publication No. 7-109317), have been applied to substrates in order to impart surface modification functions such as water-repellent and oil-repellent properties.

[0003] In this case, the active ingredient, a polymer, is often handled as a solution (water- and oil-repellent agent) dissolved in a solvent. However, if the degree of polymerization of the polymer is not reproducible, significant variations in the viscosity of the solution can occur from one manufacturing lot to the next, making it difficult to handle the water- and oil-repellent agent, including its coating properties. Therefore, a means of stably producing a polymer solution with the appropriate viscosity is necessary.

[0004] Furthermore, the heat resistance of the polymer (coating film) after coating the substrate (suppression of repelling due to heat) is also required, and there was room for improvement in conventional coating films. In addition to the above-mentioned documents, the following documents can be cited as prior art related to the present invention.

[0005] Japanese Patent Publication No. 1-42983, Japanese Patent Publication No. 7-109317, Japanese Patent Publication No. 2020-50757, International Publication No. 2007 / 086341

[0006] The present invention has been made in view of the above circumstances, and aims to provide a copolymer having a fluorine-containing monomer as a monomer component, which is excellent in terms of reproducibility of the degree of polymerization and heat resistance (particularly the heat resistance of the coating film (suppression of the occurrence of repelling due to heat)), a water-repellent and oil-repellent agent containing the copolymer, and an article having a film of the water-repellent and oil-repellent agent on its surface.

[0007] As a result of diligent research to solve the above objectives, the present inventors have found that copolymers comprising (I) a fluorine-containing monomer having a monovalent fluoropolyether group and a polymerizable group at its terminus, with the fluoropolyether group and the polymerizable group bonded directly or via a linker, and (II) a monomer having at least one polymerizable group and having a molecular weight smaller than that of the fluorine-containing monomer (I), exhibit excellent reproducibility of polymerization degree and heat resistance (particularly the heat resistance of the coating film (suppression of heat-induced repulsion)). Furthermore, they have found that a water- and oil-repellent coating containing this copolymer maintains good water- and oil-repellent properties not only initially but also under heat-resistant conditions, leading to the present invention.

[0008] Accordingly, the present invention provides the following copolymers, water-repellent and oil-repellent agents and articles: [1] A copolymer comprising (I) a fluorine-containing monomer having a monovalent fluoropolyether group and a polymerizable group at its terminus, wherein the fluoropolyether group and the polymerizable group are bonded directly or via a linker, and (II) a monomer having at least one polymerizable group and having a molecular weight smaller than that of the fluorine-containing monomer (I) as a monomer component. [2] The copolymer according to [1], wherein the number average molecular weight of the monovalent fluoropolyether group in the fluorine-containing monomer (I) is 1,000 to 5,000. [3] The copolymer according to [1] or [2], wherein the molecular weight of monomer (II) is less than 1,000. [4] The copolymer according to any one of [1] to [3], wherein monomer (II) does not contain a fluorine atom. [5] The copolymer according to any one of [1] to [4], wherein the monovalent fluoropolyether group in the fluorine-containing monomer (I) is a monovalent fluoropolyether group whose terminal end is blocked by a fluoroalkyl group having 5 or fewer carbon atoms. [6] The copolymer according to any one of [1] to [5], wherein the monovalent fluoropolyether group in the fluorine-containing monomer (I) is represented by the following average formula (1). (In the formula, k is an integer from 0 to 4, m is an integer from 1 to 5 independently for each unit, n is a positive number from 3 to 73, and p is an integer from 1 to 3. Each of these units may be linear or branched.) [7] The copolymer according to any one of [1] to [6], wherein the polymerizable group in the fluorine-containing monomer (I) is a group selected from (meth)acryloyl group, (meth)acryloyloxy group, (meth)allyl group, vinyl group, vinylene group, and vinylidene group. [8] The copolymer according to any one of [1] to [7], wherein the linker in the fluorine-containing monomer (I) is an unsubstituted or substituted divalent or greater hydrocarbon group which may contain one or more selected from an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond. [9] The copolymer according to any one of [1] to [8], wherein the fluorine-containing monomer (I) is a fluorine-containing monomer represented by the following general formula (I-1). (In the formula, Rf is a monovalent fluoropolyether group having a number average molecular weight of 1,000 to 5,000, with its terminal end sealed by a perfluoroalkyl group having 5 or fewer carbon atoms; X is an unsubstituted or substituted divalent hydrocarbon group which may contain a single bond or one or more selected from an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond; and R is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group.)

[10] The copolymer according to [9], wherein Rf in general formula (I-1) is represented by the following average formula (1). (In the formula, k is an integer from 0 to 4, m is an integer from 1 to 5 independently for each unit, n is a positive number from 3 to 73, and p is an integer from 1 to 3. Each of these units may be linear or branched.)

[11] The copolymer according to [9] or

[10] , wherein X in general formula (I-1) is selected from a single bond, an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, and a structure represented by the following general formulas (2) to (7). (In the formula, the position marked with * is the bonding site to the oxygen atom in General Formula (I-1), and the position marked with ** is the bonding site to Rf in General Formula (I-1).)

[12] The copolymer according to any one of [9] to

[11] , wherein R in General Formula (I-1) is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group or a phenyl group.

[13] The monomer (II) is an unsubstituted or substituted 2- to 4-valent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an ether bond, a carbonyl bond, an ester bond, -NR 1 - bond, -C(=O)NR 1 - bond, -OC(=O)NR 1 - bond, -NR 1 C(=O)NR 2 - bond, -NR 1 C(=O)N= bond, -C(=O)NR 1 C(=O)- bond (R 1 , R 2The copolymer according to any one of [1] to

[12] , having a 1-6 valent structure in its molecule, selected from the group consisting of a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclopentane ring, a cyclohexane ring, a benzene ring, and a nitrogen-containing 5-membered ring or nitrogen-containing 6-membered ring containing one or more nitrogen atoms in the ring structure (these ring structures may contain carbonyl bonds, and the hydrogen atoms in the ring structure may contain heteroatoms, or may be substituted by unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms or NH2 groups), and having a polymerizable unsaturated ethylene group.

[14] The copolymer according to any one of [1] to

[13] , wherein monomer (II) is copolymerized in a ratio of 0.1 to 5% by mass with respect to the total mass of fluorine-containing monomer (I) and monomer (II).

[15] A copolymer according to any one of [1] to

[14] , wherein the coefficient of variation (CV) of the kinematic viscosity of 15% by mass solvent dissolution in four synthesis lots synthesized under the same conditions is less than 50%.

[16] A water-repellent and oil-repellent agent containing the copolymer according to any one of [1] to

[15] .

[17] A water-repellent and oil-repellent agent according to

[16] , which provides a film with a water contact angle of 115° or more when applied to a glass plate.

[18] A water-repellent and oil-repellent agent according to

[16] or

[17] , which provides a film with a hexadecane contact angle of 65° or more when applied to a glass plate.

[19] A water-repellent and oil-repellent agent according to any one of

[16] to

[18] , which provides a film with an oil repellency of grade 7 or higher according to the AATCC test method 118-2020 when applied to a substrate, and whose oil repellency does not decrease from the initial oil repellency after heating at 150°C for 100 hours.

[20] An article having a film of a water-repellent or oil-repellent agent described in any of

[16] to

[19] on its surface.

[21] The article according to

[20] , wherein the article is made of fibers or a porous membrane.

[22] The article according to

[21] , wherein the fibers or porous membrane is made of fluororesin.

[0009] According to the present invention, a copolymer with excellent reproducibility of the degree of polymerization and heat resistance (particularly the heat resistance of the coating film (suppression of heat-induced repulsion)) can be obtained. A water- and oil-repellent agent containing this copolymer exhibits good water- and oil-repellent properties not only initially but also under heat-resistant conditions, resulting in a uniform coating film.

[0010] In the present invention, "(meth)acryloyl group" refers to one or both of an acryloyl (hereinafter also called acrylic) group and a methacryloyl (hereinafter also called methacrylic) group; "(meth)acryloyloxy group" refers to one or both of an acryloyloxy group and a methacryloyloxy group; and "(meth)acrylic acid" refers to one or both of acrylic acid and methacrylic acid. Furthermore, "(meth)allyl group" refers to one or both of an allyl group and a metaallyl group.

[0011] The copolymer of the present invention comprises the following fluorine-containing monomer (I) and monomer (II) as monomer components: (I) a fluorine-containing monomer having a monovalent fluoropolyether group and a polymerizable group at its terminus, wherein the fluoropolyether group and the polymerizable group are bonded directly or via a linker; and (II) a monomer having at least one polymerizable group and having a molecular weight smaller than that of fluorine-containing monomer (I).

[0012] [Fluorine-containing monomer (I)] Fluorine-containing monomer (I) has a monovalent fluoropolyether group and a polymerizable group at its terminal end, and the fluoropolyether group and the polymerizable group are bonded directly or via a linker.

[0013] In the fluorine-containing monomer (I), it is preferable to have one or two monovalent fluoropolyether groups, and it is preferable to have one.

[0014] In the fluorine-containing monomer (I), the number-average molecular weight of the monovalent fluoropolyether group is preferably 1,000 to 5,000, and more preferably 1,300 to 4,200. If the number-average molecular weight of the monovalent fluoropolyether group is less than 1,000, the heat resistance (water and oil repellency after heat resistance testing) of the coating may be poor, and if it exceeds 5,000, the viscosity is high, making it difficult to handle during polymerization, and the initial water and oil repellency and heat resistance (water and oil repellency after heat resistance testing) of the coating may be poor. In the present invention, the number-average molecular weight of the monovalent fluoropolyether group is, for example, 19 This can be determined by F-NMR, etc.

[0015] Furthermore, the molecular weight of the fluorine-containing monomer (I) is preferably 1,027 to 5,500, more preferably 1,100 to 4,400, and even more preferably 1,400 to 4,400. The molecular weight of the fluorine-containing monomer (I) can be calculated as α + β, where α is the number-average molecular weight of the monovalent fluoropolyether group and β is the molecular weight of the linker and polymerizable group. In this invention, this is referred to as the "molecular weight". Here, the molecular weight of the linker and polymerizable group can be calculated from the molecular formula.

[0016] In fluorine-containing monomers (I), the monovalent fluoropolyether group is a fluoroalkyl group with 5 or fewer carbon atoms at the end, particularly a perfluoroalkyl group, for example, CF3-, C2F5-(CF3CF2-), C3F7-(CF3CF2CF2-, (CF3)2CF-), C4F9-(CF3(CF2)3-), C5F 11 It is preferable that it is sealed with -(CF3(CF2)4-), etc.

[0017] In the fluorine-containing monomer (I), the monovalent fluoropolyether group is preferably represented by the following average formula (1). (In the formula, k is an integer from 0 to 4, preferably from 0 to 2; m is an integer from 1 to 5, preferably from 1 to 3, independently for each unit; n is a positive number from 3 to 73, preferably from 5 to 28; and p is an integer from 1 to 3, preferably 1 or 2. Each of these units may be linear or branched.)

[0018] Note that the repeating unit OC is enclosed in parentheses with n. m F 2m It may consist of a single unit, or it may consist of a combination of two or more units, and in the case of a combination of two or more units, these units may be combined randomly.

[0019] Preferably, the above formula (1) is a structure represented by the following average formulas (1-1) and (1-2). (In the formula, n1 is a positive number between 5 and 28.) (In the formula, n² is a positive number between 0 and 41, n³ is a positive number between 0 and 73, and n² + n³ = a number between 8 and 73. Each repeating unit shown in the parentheses with n² and n³ may be combined randomly.)

[0020] More preferably, the structure represented by the following formulas (1-3) is the above formula (1).

[0021] In the fluorine-containing monomer (I), it is preferable to have one or two polymerizable groups, and it is preferable to have one.

[0022] Examples of polymerizable groups in the fluorine-containing monomer (I) include (meth)acryloyl group, (meth)acryloyloxy group, (meth)allyl group, vinyl group, vinylene group, and vinylidene group, with (meth)acryloyloxy group being preferred.

[0023] In the fluorine-containing monomer (I), the linker may contain one or more selected from an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond, and is preferably an unsubstituted or substituted divalent or greater hydrocarbon group, more preferably a divalent hydrocarbon group.

[0024] The fluorine-containing monomer (I) is preferably a fluorine-containing monomer represented by the following general formula (I-1). (In the formula, Rf is a monovalent fluoropolyether group with a number-average molecular weight of 1,000 to 5,000, terminated by a perfluoroalkyl group having 5 or fewer carbon atoms; X is an unsubstituted or substituted divalent hydrocarbon group which may contain a single bond or one or more selected from an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond; and R is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group.)

[0025] In the above formula (I-1), Rf is a monovalent fluoropolyether group with a number-average molecular weight of 1,000 to 5,000, terminated by a perfluoroalkyl group having 5 or fewer carbon atoms, preferably represented by the above formula (1), and examples of those represented by formula (1) are the same as those described above.

[0026] In the above formula (I-1), the number-average molecular weight of Rf is 1,000 to 5,000, preferably 1,300 to 4,200. If the number-average molecular weight of Rf is less than 1,000, the heat resistance (water and oil repellency after heat resistance testing) of the coating may be poor, and if it exceeds 5,000, the viscosity is high, making it difficult to handle during polymerization, and the initial water and oil repellency and heat resistance (water and oil repellency after heat resistance testing) of the coating may be poor. In the present invention, the number-average molecular weight of Rf is, for example, 19 This can be determined by F-NMR, etc.

[0027] In general formula (I-1), X is a single bond, or an unsubstituted or substituted divalent hydrocarbon group which may contain one or more selected from an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond, and is a linking group (linker) between Rf and the acrylic acid ester group. Examples of unsubstituted or substituted divalent hydrocarbon groups which may contain one or more selected from an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond include alkylene groups such as a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), a hexamethylene group, an octamethylene group, an arylene group such as a phenylene group, or a combination of two or more of these groups (alkylene-arylene group, etc.), etc., having 1 to 1 carbon atoms. 20. Preferably, divalent hydrocarbon groups having 1 to 15 carbon atoms are mentioned, and the divalent hydrocarbon groups having 1 to 20 carbon atoms may include one or more selected from ether bonds (-O- (oxygen atom)), amino bonds (-NH-), amide bonds (-C(=O)NH-), urethane bonds (-OC(=O)NH-), and urea bonds (-NHC(=O)NH-), and may also be substituted divalent hydrocarbon groups in which some or all of the hydrogen atoms bonded to the carbon atoms are replaced with halogen atoms such as iodine, excluding fluorine. The above divalent hydrocarbon groups having 1 to 20 carbon atoms may also include bonds in which two amide bonds are repeated.

[0028] X is preferably a single bond, an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, and any of the structures represented by the following general formulas (2) to (7). (In the formula, the parts indicated by * are the bonding sites with the oxygen atom in general formula (I-1), and the parts indicated by ** are the bonding sites with Rf in general formula (I-1).)

[0029] In the above formula (I-1), R is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. Examples of halogen atoms, alkyl groups, or aryl groups include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, methyl groups, and phenyl groups. Preferably, R is a hydrogen atom or a methyl group.

[0030] Examples of fluorine-containing monomers represented by the above formula (I-1) include those represented by the following formula. (In the formula, n1, n2, and n3 are the same as above. Each repeating unit shown in the parentheses with n2 and n3 may be combined randomly.)

[0031] [Method for preparing fluorine-containing monomer (I)] One method for preparing the fluorine-containing monomer (I) represented by the above formula (I-1) is, for example, to reduce a fluoropolyether compound having a C(=O)F group or a carboxyl group at one end to a fluoropolyether compound having a hydroxyl group at the other end, and to react it with an isocyanate compound having an acryloyl group or a methacryloyl group. Specifically, a fluoropolyether compound having a C(=O)F group or a carboxyl group at one end can be aged with a solvent, such as tetrahydrofuran, and a toluene solution of a reducing agent, such as sodium bis(2-methoxyethoxy)aluminum hydride, at a temperature of 25 to 60°C, preferably 35 to 55°C, for 4 to 24 hours, preferably 10 to 20 hours, to obtain a fluoropolyether compound having a hydroxyl group at one end. The obtained fluoropolyether compound having a hydroxyl group at one end is mixed with a polymerization inhibitor, such as 4-methoxyphenol, heated at a temperature of 25 to 55°C, preferably 40 to 50°C, then a catalyst, such as tetrakis(2-ethylhexyl) orthotitanate, is added, followed by the dropwise addition of 2-isocyanatoethyl acrylate, and the mixture is aged at a temperature of 25 to 55°C, preferably 40 to 50°C, for 2 to 24 hours, preferably 2 to 10 hours, to obtain the fluorine-containing monomer represented by the above formula (I-1). 2-isocyanatoethyl methacrylate may be used instead of 2-isocyanatoethyl acrylate.

[0032] [Monomer (II)] Monomer (II) has at least one polymerizable group and a molecular weight smaller than that of fluorine-containing monomer (I). Preferably, monomer (II) does not contain a fluorine atom.

[0033] The molecular weight of monomer (II) is smaller than that of fluorine-containing monomer (I), preferably less than 1,000, and more preferably between 100 and 600. The molecular weight of monomer (II) can be calculated from its molecular formula.

[0034] In monomer (II), there is one or more polymerizable groups, preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, particularly preferably 2 or 3, and especially preferably 3. Water and oil repellency and the reproducibility of the degree of polymerization can be adjusted by the number of polymerizable groups.

[0035] In monomer (II), the polymerizable group is preferably a polymerizable unsaturated ethylene group. Specifically, examples include vinyl group, vinylene group, vinylidene group, (meth)allyl group, (meth)acryloyl group, and (meth)acryloyloxy group, with (meth)acryloyloxy group being more preferred among these.

[0036] Monomer (II) contains unsubstituted or substituted C1-C10 divalent-tetravalent saturated aliphatic hydrocarbon groups, ether bonds, carbonyl bonds, ester bonds, and -NR 1 -bond, -C(=O)NR 1 -bond, -OC(=O)NR 1 -bond, -NR 1 C(=O)NR 2 -bond, -NR 1 C(=O)N=bond, -C(=O)NR 1 C(=O)-bond (R 1 , R 2 It is preferable that the molecule has a 1-6 valent, preferably 1-3 valent structure selected from the group consisting of a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclopentane ring, a cyclohexane ring, a benzene ring, and a nitrogen-containing 5-membered ring or nitrogen-containing 6-membered ring containing one or more nitrogen atoms in the ring structure (these ring structures may contain carbonyl bonds, and the hydrogen atoms in the ring structure may contain heteroatoms, or may be substituted by unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms or NH2 groups).

[0037] Here, R 1 , R 2Each of these is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of monovalent hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenylethyl groups. 1 , R 2 Hydrogen atoms and methyl groups are preferred as these elements.

[0038] Examples of nitrogen-containing five-membered rings containing one or more nitrogen atoms in the ring structure include pyrrolidine rings, pyrroline rings, and pyrrole rings having one nitrogen atom; pyrazolidine rings, imidazolidine rings, pyrazoline rings, imidazoline rings, pyrazole rings, and imidazole rings having two nitrogen atoms; 1,2,3-triazolidine rings, 1,2,4-triazolidine rings, 1,2,3-triazoline rings, 1,2,4-triazoline rings, 1,2,3-triazole rings, and 1,2,4-triazole rings having three nitrogen atoms; and tetrazolidine rings, tetrazoline rings, and tetraazole rings having four nitrogen atoms.

[0039] The nitrogen-containing five-membered ring may contain a carbonyl bond in its structure. Examples include a 2-pyrrolidone ring, a 3-pyrrolidone ring, a succinimide ring, a 2,3-pyrrolidinedione ring, a 2,4-pyrrolidinedione ring, a maleimide ring, a 3,5-pyrazolidinedione ring, a pyrazolidine-3,4,5-trione ring, a hydantoin ring, an imidazolidine-2,4,5-trione ring, a 1,2,3-triazolidine-4,5-dione ring, and a urazole ring.

[0040] Here, examples of nitrogen-containing six-membered rings containing one or more nitrogen atoms in the ring structure include piperidine rings, piperidine rings, and pyridine rings having one nitrogen atom; 1,2-diadinane rings, 1,3-diadinane rings, piperazine rings, pyridazine rings, pyrimidine rings, and pyrazine rings having two nitrogen atoms; and 1,2,3-triazinane rings, 1,2,4-triazinane rings, and 1,3,5-triazinane rings having three nitrogen atoms. Examples include 1,2,3-triazine rings, 1,2,4-triazine rings, 1,3,5-triazine rings, 1,2,3,4-tetradinane rings with four nitrogen atoms, 1,2,3,5-tetradinane rings, 1,2,4,5-tetradinane rings, 1,2,3,4-tetradinane rings, 1,2,3,5-tetradinane rings, 1,2,4,5-tetradinane rings, pentadinane rings with five nitrogen atoms, and pentadine rings.

[0041] The nitrogen-containing six-membered ring may contain carbonyl bonds in its structure, for example, a 2-piperidone ring, a glutarimide ring, a 2,4,6-piperidinetrione ring, a 1,2-diadinane-3-one ring, a 1,3-diadinane-4-one ring, a dihydrouracil ring, a 1,3-diadinane-4,6-dione ring, a 1,3-diadinane-2,4,5-trione ring, a 1,3-diadinane-2,4,6-trione ring, an alloxane ring, or a piperazi Examples include non-cyclic rings, 2,3-piperazinedinone rings, 2,5-piperazinedione rings, 2,6-piperazinedinone rings, 2,3,5-piperazinentrion rings, 2,3,5,6-piperazinetetraone rings, 1,2,4-triazine-3,5-dione rings, 1,2,4-triazine-3,5,6-trione rings, 1,3,5-triazine-2-one rings, 1,3,5-triazine-2,4-dione rings, isocyanuric rings, and so on.

[0042] Examples of monomers (II) include isoprene, butadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, vinylcyclopentane, styrene, N-phenylacrylamide, cyclopentadiene, cyclohexadiene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene, allyl ether, 1,4-cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene divinyl ether, divinyl adipate, diallyl oxalate, diallyl maleate, diallyl adipate, 1,4-cyclohexanedicarboxylic acid diallyl, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, ethylene glycol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 2,2-dimethyl-1,3-propanediol diacrylate, 1,6-hex Examples include sandiol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, tricyclodecanol diacrylate, bisphenol A diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and those in which the allyl portion corresponds to methallyl and the acrylate (acrylic) portion corresponds to methacrylate (methacrylic).

[0043] Furthermore, examples of monomer (II) include 3-vinylpyrrolidine, 1-vinyl-2-pyrrolidone, 5-vinylpyrrolidone, 1-vinyl-1H-pyrrole, 2-vinylpyrrole, 1-vinylpiperazine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinyl-4,6-diamino-1,3,5-triazine, 2-allylpyrrolidine, 1-allylpiperazine, 2-allylpyridine, 3-allylpyridine, 4-allylpyridine, diallylamine, allyl isocyanurate, 1-allyl-3,5-dipropyl isocyanurate, 1,3-diallyl isocyanurate, 1,3-diallyl-5-propyl isocyanurate, 1,3,5-trialyl isocyanurate, and N-(2-acryloyloxyethyl)pyrrolidone. N-(2-acryloyloxyethyl)succinimide, N-succinimidyl acrylate, N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide, 1,4-bis(acryloyl)piperazine, 2-acryloyloxyethyl isocyanurate, bis(2-hydroxyethyl)-2-acryloyloxyethyl isocyanurate, bis(2-acryloyloxyethyl) isocyanurate, 1,3-bis(acryloyloxyethyl)urea, bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, tris(2-acryloyloxyethyl) isocyanurate, or the compound of formula (8) below. In addition to N-[tris(3-acrylamidopropoxymethyl)methyl]acrylamide, other examples include those in which the allyl portion corresponds to methallyl and the acrylate (acrylic, acryloyl) portion corresponds to methacrylate (methacrylic, methacryloyl).

[0044] Furthermore, monomer (II) may be used alone or in combination of two or more types.

[0045] The amount of monomer (II) used is preferably 0.1 to 5% by mass (0.1% to 5% by mass) relative to the total mass of fluorine-containing monomer (I) and monomer (II), more preferably 0.1% to less than 5% by mass, even more preferably 0.1% to 4% by mass, and particularly preferably 0.5% to 4% by mass. If the amount of monomer (II) used is less than 0.1% by mass, the degree of polymerization may not be reproducible, and if the amount of monomer (II) used exceeds 5% by mass, the solubility in the solvent decreases, which may result in copolymer precipitation or gelation, making it impossible to obtain a copolymer solution.

[0046] The amount of polymerizable groups in monomer (II) is preferably 1 mol% to 40 mol%, more preferably 3 mol% to 35 mol%, and even more preferably 5 mol% to 30 mol%, relative to the total amount of polymerizable groups in fluorine-containing monomer (I) and monomer (II). If the amount of polymerizable groups in monomer (II) is less than 1 mol%, the degree of polymerization may not be reproducible, or the heat resistance of the coating film (suppression of heat-induced repulsion) may be poor. If the amount of polymerizable groups in monomer (II) exceeds 40% by mass, the solubility in the solvent decreases, which may result in copolymer precipitation or gelation, making it impossible to obtain a copolymer solution.

[0047] [Method for producing the copolymer] The copolymer of the present invention can be obtained by polymerizing predetermined amounts of a fluorine-containing monomer (I) and monomer (II) using a solvent and a radical polymerization initiator by a known method such as solution polymerization.

[0048] The solvent used in the method for producing the copolymer of the present invention is not particularly limited as long as it can dissolve the fluorine-containing monomer (I), but a fluorine-based solvent is preferred. Examples of fluorine-based solvents include Novec 7300, Novec 7200, Novec 7100 (manufactured by 3M Limited), AC-6000, AE-3000 (manufactured by AGC Inc.), hexafluoroacetone, hexafluoroisopropanol, and m-xylene hexafluoride (manufactured by Central Glass Co., Ltd.). Among these, Novec 7300, or a mixed solvent of m-xylene hexafluoride and Novec 7300, is preferable from the viewpoint of solubility. The content of m-xylene hexafluoride in this mixed solvent is preferably 0.1% to 70% by mass, more preferably 0.5% to 65% by mass, even more preferably 1% to 60% by mass, and particularly preferably 1% to 55% by mass, based on the total mass of m-xylene hexafluoride and Novec 7300. The amount of solvent used is not particularly limited, but it is preferably 50 to 2,000 parts by mass, particularly 100 to 1,000 parts by mass, and even more preferably 125 to 400 parts by mass, based on 100 parts by mass of the total of fluorine-containing monomer (I) and monomer (II).

[0049] Examples of radical polymerization initiators used in the copolymer production method of the present invention include dimethyl azobisisobutyrate (V-601), cumene hydroperoxide, succinate peroxide, di-t-butyl peroxide, diisobutyryl peroxide, diisobutyl peroxydicarbonate, dicumyl peroxide, cyclohexanone peroxide, dimethyl-2,2'-azobisisobutyrate, benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, 2,2'-azobis(2-methylamidooxime) dihydrochloride, 2,2'-azobis(2-methylbutyronitrile) (V-59), 2,2'-azobis(isobutylamidine) dihydrochloride, and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] Examples include azo compounds such as 1,2'-azobisisobutyronitrile (AIBN), 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne-3, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethylhexane-2,5-dihydroperoxide, t-butyl-α-cumylperoxide, t-butylperoxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxyisopropyl carbonate, t-butylhydroperoxide, α,α'-bis(t-butylperoxy)-p-diisopropylbenzene, organic peroxides, potassium persulfate, sodium persulfate, and ammonium persulfate. These radical polymerization initiators may be used individually or in combination of two or more types. The amount of radical polymerization initiator used is not particularly limited, but it is preferably 0.05 to 10 parts by mass, and especially 0.1 to 3 parts by mass, per 100 parts by mass of the total of fluorine-containing monomer (I) and monomer (II).

[0050] In the polymerization method using the above solvent and radical polymerization initiator, the polymerization conditions for fluorine-containing monomer (I) and monomer (II) are preferably 40 to 120°C, particularly 65 to 70°C, under an inert gas atmosphere for 4 to 30 hours, and especially 18 to 24 hours.

[0051] The copolymer of fluorine-containing monomer (I) and monomer (II) obtained in this manner has a kinematic viscosity of 1 to 150 mmHg when dissolved in a 15% by mass solvent. 2 It is preferable that it be / s, and 5 to 80 mm 2 It is more preferable that the kinematic viscosity is 1 / s. If the kinematic viscosity is too low, the surface properties when coated onto the substrate may be poor, and if it is too high, the workability during coating may be poor. The kinematic viscosity can be measured at 25°C using a Cannon-Fenske viscometer by the method described in JIS Z8803:2011. The solvent is not particularly limited as long as it can dissolve the copolymer of fluorine-containing monomer (I) and monomer (II), but fluorine-based solvents are preferred in terms of solubility and stability. Examples of fluorine-based solvents include Novec 7300, Novec 7200, Novec 7100 (manufactured by 3M Limited), AC-6000, AE-3000 (manufactured by AGC Inc.), hexafluoroacetone, hexafluoroisopropanol, and m-xylene hexafluoride (manufactured by Central Glass Co., Ltd.). In particular, from the viewpoint of solubility, Novec7300 or a mixed solvent of m-xylene hexafluoride and Novec7300 is preferred. The content of m-xylene hexafluoride in this mixed solvent is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 65% by mass or less, even more preferably 1% by mass or more and 60% by mass or less, and especially preferably 1% by mass or more and 55% by mass or less, based on the total mass of m-xylene hexafluoride and Novec7300.

[0052] Furthermore, for copolymers of fluorine-containing monomer (I) and monomer (II), the coefficient of variation (CV) of the kinematic viscosity at which the 15% by mass solvent dissolves in four synthesis lots synthesized under the same conditions is preferably less than 50%, and more preferably less than 35%. If the coefficient of variation (CV) of the kinematic viscosity at which the 15% by mass solvent dissolves in four synthesis lots is less than 50%, it can be determined that the degree of polymerization is reproducible for each manufacturing lot. If the coefficient of variation (CV) of the kinematic viscosity at which the 15% by mass solvent dissolves in four synthesis lots is 50% or more, there will be a large variation in the viscosity of the solution for each manufacturing lot, which may make it difficult to handle. The coefficient of variation (CV) of the kinematic viscosity at which the 15% by mass solvent dissolves in four synthesis lots is less than 50%, and more preferably less than 35%. 2 / s)] / [Average dissolution kinematic viscosity (mm 2 / s)] × 100 In order to make the coefficient of variation (CV) of the kinematic viscosity of 15% by mass solvent dissolution less than 50% in four synthesis lots of the copolymer of the present invention synthesized under the same conditions, it is preferable to copolymerize with monomer (II) having a smaller molecular weight than monomer (I) having a fluoropolyether group. In the homopolymerization of monomer (I) having a bulky fluoropolyether group alone, collisions of radicalized polymerizable groups cannot be controlled due to steric hindrance, which may result in variations in the degree of polymerization. It is thought that by adding monomer (II) with a smaller molecular weight to the system, the effect of steric hindrance is reduced and the reproducibility of the degree of polymerization is improved.

[0053] The copolymer of the present invention exhibits high reproducibility in the degree of polymerization and reduces variations in the viscosity of the solution from one manufacturing lot to the next. As a result, the coating properties of the water-repellent and oil-repellent agents described later become more stable and easier to handle.

[0054] On the other hand, conventionally, compounds having long-chain perfluoroalkyl groups with eight or more carbon atoms have been used to exhibit surface modification functions such as high water-repellent and oil-repellent properties. However, long-chain perfluorocarboxylic acids having perfluoroalkyl groups with eight or more carbon atoms, including perfluorooctanoic acid (PFOA), have been noted to accumulate in the human body. To reduce such risks to living organisms and the environment, PFOA has been replaced with, for example, perfluorohexanoic acid (PFHxA) with six carbon atoms. For example, Patent Document 3 (Japanese Patent Application Publication No. 2020-50757) discloses a surface modifier in which a polymer of a (meth)acrylic acid derivative containing a perfluoroalkyl group with six carbon atoms is used as an active ingredient. However, similar risks remain a concern with PFHxA as well.

[0055] When the copolymer of the present invention is used in which the terminal ends of the monovalent fluoropolyether groups contained therein are sealed with fluoroalkyl groups having 5 or fewer carbon atoms, it may be possible to maintain high water-repellent and oil-repellent properties and other surface modification functions while not containing substances that have been pointed out as accumulating in the human body and the environment.

[0056] [Water- and oil-repellent agent] The water- and oil-repellent agent of the present invention contains a copolymer of the above-mentioned fluorine-containing monomer (I) and monomer (II). The water- and oil-repellent agent of the present invention is usually provided as a solvent solution of the above copolymer. Here, the amount of copolymer in the solvent solution (concentration of copolymer) is preferably 1 to 50% by mass, particularly 3 to 30% by mass, and especially 3 to 15% by mass.

[0057] The solvent used in the water-repellent and oil-repellent agent is not particularly limited as long as it can dissolve the copolymer, but a fluorine-based solvent is preferred. Examples of fluorine-based solvents include Novec 7300, Novec 7200, Novec 7100 (manufactured by 3M Limited), AC-6000, AE-3000 (manufactured by AGC Inc.), hexafluoroacetone, hexafluoroisopropanol, and m-xylene hexafluoride (manufactured by Central Glass Co., Ltd.). Among these, Novec 7300, or a mixed solvent of m-xylene hexafluoride and Novec 7300, is preferable from the viewpoint of solubility. The solvent used in the above copolymer manufacturing method may be used as the solvent for the water-repellent and oil-repellent agent, or the above solvent may be further added after the copolymer is manufactured in order to adjust the copolymer's concentration.

[0058] The application method for the water-repellent and oil-repellent agent of the present invention to a substrate can include, for example, a spin coating method, a dip coating method, a spray coating method, a roll coating method, a meniscus coating method, or a screen printing method.

[0059] Examples of substrates to which the water-repellent and oil-repellent agent of the present invention is applied include glass, fibers, and porous membranes, with fibers and porous membranes being preferred, and fibers or porous membranes made of fluororesin being more preferred.

[0060] Examples of fibrous substrates to which the water-repellent and oil-repellent agent of the present invention is applied include fibers, yarns, and cloths. Examples of fibers constituting the fibrous substrate include glass fibers, carbon fibers, aramid fibers, polyethylene fibers, polytetrafluoroethylene (PTFE) fibers, Zylon fibers, boron fibers, basalt fibers, metal fibers, polyamide fibers, silicon carbide fibers, polyester fibers, ceramic fibers, alumina fibers, mineral fibers, rock fibers, slug fibers, polyoxymethylene fibers, aromatic polyamide fibers, poly(p-phenylenebenzobisoxazole) fibers, plant fibers, cellulose fibers, and lignin fibers. These fibers may be used individually or in combination of two or more types.

[0061] Examples of porous membrane substrates to which the water-repellent and oil-repellent agent of the present invention is applied include nonwoven fabrics, perforated membranes, microporous membranes, and porous bodies. Examples of materials constituting the porous membrane substrate include resins such as PTFE (polytetrafluoroethylene), ceramics, and metals, with PTFE (polytetrafluoroethylene) being preferred.

[0062] Because the water- and oil-repellent agent of the present invention contains fluorine atoms in the copolymer, it exhibits excellent water- and oil-repellent properties and can be used as a water- and oil-repellent coating agent for glass, fibers, porous membranes, and especially fibers and porous membranes. In particular, while it is difficult to further improve the performance of fibers and porous membranes composed of fluororesins, which already have high water- and oil-repellent properties, the water- and oil-repellent agent of the present invention can improve their performance, making it useful for application to fibers and porous membranes composed of fluororesins.

[0063] The water- and oil-repellent agent of the present invention can easily form a film on the substrate surface by drying the solvent after coating the substrate. Specifically, it is preferable to dry it at room temperature (25°C ± 10°C) for 30 minutes to 24 hours. In order to speed up the drying, heating may be performed at, for example, 40 to 150°C for about 30 seconds to 24 hours, within a range that does not affect the substrate.

[0064] The film thickness is selected appropriately depending on the type of substrate, but is usually 0.01 to 50 μm, and particularly 0.1 to 10 μm. The film thickness when applied to a smooth substrate such as glass can be calculated, for example, using the following formula: [Film Thickness (μm)] = [Increase in Substrate Mass Before and After Coating (g)] ÷ [Density of Water-Repellent and Oil-Repellent Agent (g / cm³)] 3 )]÷[Substrate area (cm 2 ) ÷ 2 × 10,000

[0065] Furthermore, the amount of coating applied to a substrate into which the water-repellent and oil-repellent agent penetrates, such as fibers or porous membranes, can be calculated, for example, by the following formula: [Amount of coating (mass%)] = [Increase in substrate mass before and after coating (g)] ÷ [Substrate mass before coating (g)] × 100 The amount of coating calculated by the above formula is usually 0.1 to 25 mass%, and especially 1 to 15 mass%.

[0066] Furthermore, film thickness can also be measured by methods such as spectral reflectance measurement, X-ray reflectance measurement, spectral ellipsometry measurement, and X-ray fluorescence measurement.

[0067] It is preferable that the water-contact angle (water contact angle) of the film formed by coating a glass plate with the water-repellent and oil-repellent agent of the present invention is 115° or more, preferably 125° or more, at a temperature of 25°C and a relative humidity of 40%. In this invention, the water-contact angle is the value measured using a Drop Master contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) under the condition of a 2 μL droplet. In order to achieve the above water-contact angle (water contact angle) of 115° or more, it is preferable that the copolymer contained in the water-repellent and oil-repellent agent has a number-average molecular weight of 1,000 or more of the monovalent fluoropolyether groups in the fluorine-containing monomer (I), and that monomer (II) is copolymerized in a ratio of 5% by mass or less of the total mass of monomer (I) and monomer (II).

[0068] Furthermore, it is preferable that the contact angle with hexadecane (hexadecane (HD) contact angle) of the film formed by coating a glass plate with the water- and oil-repellent agent of the present invention at a temperature of 25°C and a relative humidity of 40% is 65° or more, preferably 75° or more. In this invention, the contact angle with hexadecane is the value measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) under the condition of a droplet of 2 μL. In order to achieve the above contact angle with hexadecane (hexadecane (HD) contact angle) of 65° or more, it is preferable that the copolymer contained in the water- and oil-repellent agent has a number-average molecular weight of 1,000 or more of the monovalent fluoropolyether group in the fluorine-containing monomer (I), and that monomer (II) is copolymerized in a ratio of 5% by mass or less of the total mass of monomer (I) and monomer (II).

[0069] Furthermore, it is preferable that the film formed using the water- and oil-repellent agent of the present invention has an oil repellency of grade 7 or higher according to the AATCC test method 118-2020, and that the oil repellency does not decrease from the initial oil repellency after heating at 150°C for 100 hours. In order to achieve the above oil repellency of grade 7 or higher and the oil repellency not decreasing from the initial oil repellency after heating at 150°C for 100 hours, it is preferable to use a copolymer contained in the water- and oil-repellent agent in which the number average molecular weight of the monovalent fluoropolyether group in the fluorine-containing monomer (I) is 1,000 to 5,000.

[0070] [Articles] Examples of articles having a film of the water-repellent and oil-repellent agent of the present invention on their surface include automotive products, textile products, nonwoven fabrics, fibers or porous membranes used in the presence of organic solvent liquids or their vapors, and in particular, filtration materials composed of fluororesins.

[0071] The present invention will be specifically described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following synthesis examples and examples. In the following examples, the number average molecular weight of the fluoropolyether group (Rf in general formula (I-1)) is 19 The values ​​shown are calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure based on F-NMR analysis, and the terminal group concentration is, 19 The value was calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure based on F-NMR analysis, or using dimethyl sulfoxide as a standard substance. 1The values ​​shown are calculated from the ratio of characteristic peak intensity between the terminal structure and the standard substance based on 1H-NMR analysis. The molecular weight of compound (A) is shown as the number-average molecular weight of the fluoropolyether group (Rf in general formula (I-1)) and the value calculated from the molecular formulas of the linker and polymerizable group. The molecular weight of compound (B) is shown as the value calculated from the molecular formula. The mol content of each compound is calculated by dividing the measured mass by the molecular weight calculated from the molecular formula, or by multiplying it by the terminal group concentration and then dividing the result by the number of terminal groups. The mol content of the polymerizable group is shown as the value calculated by dividing the measured mass by the molecular weight calculated from the molecular formula and multiplying that by the number of polymerizable groups assumed from the structure, or by multiplying the measured mass by the terminal group concentration. The kinematic viscosity (hereinafter referred to as "kinematic viscosity") of the monomer copolymer was measured at 25°C using a Cannon-Fenske viscometer (Cannon-Fenske SO 026110 series, manufactured by Shibata Scientific Co., Ltd.) according to the method described in JIS Z8803:2011. The film thickness of the coating on the glass sample is given by the following formula: [Film thickness (μm)] = [Increase in substrate mass before and after coating (g)] ÷ [Density of water-repellent and oil-repellent agent (g / cm³)] 3 )]÷[Substrate area (cm 2 The value shown is calculated from [(mass%)] ÷ 2 × 10,000, and the coating amount on the PTFE sample is the value measured using the following formula. The room temperature is 25°C. [Coating amount (mass%)] = [Increase in substrate mass before and after coating (g)] ÷ [Substrate mass before coating (g)] × 100

[0072] [Synthesis Example 1] Synthesis of compound (a-2) A 2 L four-necked flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, stirring blades and stirring motor is prepared using the following formula (a-1) The compound represented by (number average molecular weight of fluoropolyether group: approximately 1,450, terminal group (F in C(=O)F group) concentration: 6.69 × 10⁻¹⁴) -41000.0 g (0.669 mol) of sodium bis(2-methoxyethoxy)aluminum hydride (70% by mass toluene solution), 295.4 g (1.02 mol), and 250.0 g of tetrahydrofuran (super-dehydrated, stabilizer-free) as a solvent were charged and aged at 55°C for 20 hours. After that, the reaction was stopped, the solvent was removed by distillation under reduced pressure, and 895.9 g of the product was obtained.

[0073] The resulting product is 1 H-NMR and 19 F-NMR confirmed that the compound is represented by the following formula (a-2).

[0074] [Synthesis Example 2] Synthesis of compound (A) A 500 mL four-necked flask equipped with a thermometer, dry air inlet, reflux condenser, stirring blades and stirring motor is prepared using the following formula (a-2) The compound represented by (number-average molecular weight of fluoropolyether group: approximately 1,450, terminal group (OH group) concentration: 6.51 × 10⁻¹⁰ -4 400.0 g (0.260 mol) of 4-methoxyphenol was mixed with 0.08 g of 4-methoxyphenol. The mixture was heated to 45°C, and 0.96 g (1.70 × 10) of tetrakis(2-ethylhexyl) orthotitanate was added. -3 After adding (mol), 44.1 g (0.312 mol) of 2-isocyanatoethyl acrylate was added dropwise over 30 minutes, and the mixture was aged at 45°C for 3 hours. Then, water was added to precipitate unreacted material, which was removed by filtration to obtain 411.7 g of product.

[0075] The resulting product is 1 H-NMR and 19 F-NMR confirmed that the compound is represented by the following formula (A).

[0076] [Synthesis Example 3] Synthesis of compound (b-1) 500 mL four-necked flask equipped with a thermometer, dry air inlet, reflux condenser, stirring bar, and stirrer was charged with 50.0 g (0.354 mol) of 2-isocyanatoethyl acrylate and 150.0 g of tetrahydrofuran as a solvent. 10.0 g (0.556 mol) of water was added while stirring, and the mixture was aged at 40°C for 20 hours. The solvent was then removed by distillation under reduced pressure, and the resulting crude product was recrystallized and purified with ethanol to obtain 30.8 g of the product.

[0077] The resulting product is 1 H-NMR and 19 F-NMR confirmed that the compound is represented by the following formula (b-1).

[0078] [Synthesis Example 4] Synthesis of compound (B) with compound (b-2) as the main component A 100 mL four-necked flask equipped with a thermometer, dry air inlet, reflux condenser, stirring bar and stirrer is prepared with the following formula (b-1) 20.0 g (7.81 × 10) of the compound represented by -2 mol), 2-isocyanatoethyl acrylate 13.2 g (9.37 x 10) -2 0.01 g of 4-methoxyphenol (mol) was mixed with the mixture. The temperature was raised to 90°C, and 0.11 g of Orgatic ZC-200 (manufactured by Matsumoto Fine Chemical Co., Ltd.) was added, followed by aging at 100°C for 1 hour. Then, 33.2 g of the solvent m-xylene hexafluoride was added and dissolved, and the mixture was filtered to obtain 50.5 g of a 50% by mass solution of m-xylene hexafluoride as the product.

[0079] The resulting product solution is 1 H-NMR and 19 F-NMR confirmed that the solution was a 50% by mass solution of m-xylenehexafluoride of compound (B), whose main component is the compound represented by the following formula (b-2).

[0080] [Synthesis Example 5] Synthesis of compound (c-2) A 200 mL four-necked flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, stirring bar, and stirrer was prepared using the following formula (c-1) The compound represented by (number average molecular weight of fluoropolyether group: approximately 5,810, terminal group (F in C(=O)F group) concentration: 3.39 × 10) -4 mol / g) 100.0g (1.70×10 -2 8.5 g (0.139 mol) of ethanolamine and 100.0 g of m-xylene hexafluoride as a solvent were mixed. The mixture was aged at 65°C for 8 hours. After washing the resulting reaction solution with water, 94.4 g of the product was obtained by distillation under reduced pressure.

[0081] The resulting product is 1 H-NMR, 19 F-NMR and IR confirmed that the compound is represented by the following formula (c-2).

[0082] [Synthesis Example 6] Synthesis of compound (c-3) A 100 mL four-necked flask equipped with a thermometer, dry air inlet, reflux condenser, stirring bar and stirrer was prepared using the following formula (c-2) The compound represented by (number-average molecular weight of fluoropolyether group: approximately 5,810, terminal group (OH group) concentration: 3.26 × 10⁻¹⁶) -4 mol / g) 50.0g (8.15×10 -3 Mix 0.005 g of 4-methoxyphenol (mol). Heat to 60°C, add 0.075 g of K-KAT XK-640 (manufactured by Kusumoto Chemical Co., Ltd.), then add 2.19 g of 2-isocyanatoethyl acrylate (1.55 x 10). -2 The mol (1) was added dropwise over 3 minutes, and the mixture was aged at 60°C for 6 hours. After that, it was cooled to room temperature, stirred for 12 hours, and then filtered to obtain 42.3 g of the product.

[0083] The resulting product is 1 H-NMR, 19 F-NMR and IR confirmed that the compound is represented by the following formula (c-3).

[0084] [Example 1] A 100 mL four-necked flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, stirring bar, and stirrer was prepared using the following formula (A) obtained in Synthesis Example 2 above. The monomer represented by (general formula (I-1)) has a number-average molecular weight of Rf: approximately 1,450, and a terminal group (acryloyloxy group) concentration of 6.24 × 10⁻¹⁴. -4 mol / g, molecular weight: approximately 1622.16) 19.39g (compound mol amount: 1.21 x 10 -2 mol, polymerizable group mol amount: 1.21×10 -2 mol), N-succinimidyl acrylate (molecular weight: 169.14) 0.614 g (mol amount of compound: 3.63 × 10) -3 mol, polymerizable group mol amount: 3.63×10 -3 mol), 15.0 g of m-xylene hexafluoride as a solvent, 15.0 g of Novec 7300 (manufactured by 3M Co., Ltd., C2F5-CF(OCH3)-CF(CF3)2), and 0.100 g (5.20 x 10) of V-59 (2,2'-azobis(2-methylbutyronitrile)) as a radical polymerization initiator. -4 A mol (unit) was added and reacted at 65°C for 20 hours while aeration with nitrogen gas was performed. Then, Novec 7300 was added to achieve an active ingredient concentration of 15% by mass, and a coating solution of a copolymer of the monomer represented by formula (A) and N-succinimidyl acrylate was prepared. The kinematic viscosity of the resulting copolymer was 7.35 mm. 2 It was / s.

[0085] [Example 2] A 100 mL four-necked flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, stirring bar, and stirrer was prepared using the following formula (A) obtained in Synthesis Example 2 above. The monomer represented by (general formula (I-1)) has a number-average molecular weight of Rf: approximately 1,450, and a terminal group (acryloyloxy group) concentration of 6.24 × 10⁻¹⁴. -4 mol / g, molecular weight: approximately 1622.16) 19.72 g (compound mol amount: 1.23 x 10 -2 mol, polymerizable group mol amount: 1.23×10 -2 0.278 g of 1,6-hexanediol diacrylate (molecular weight: 226.27) (mol amount of compound: 1.23 × 10⁻⁶) -3 mol, polymerizable group mol amount: 2.46×10 -3mol), 30.0 g of Novec 7300 (manufactured by 3M Co., Ltd.) as a solvent and 0.100 g of V-59 (2,2'-azobis(2-methylbutyronitrile)) as a radical polymerization initiator (5.20 x 10) -4 A mol (unit) was added and reacted at 65°C for 20 hours while aeration with nitrogen gas was performed. Then, Novec 7300 was added to achieve an active ingredient concentration of 15% by mass, and a coating solution of a copolymer of the monomer represented by formula (A) and 1,6-hexanediol diacrylate was prepared. The kinematic viscosity of the resulting copolymer was 17.3 mm. 2 It was / s.

[0086] [Example 3] A 100 mL four-necked flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, stirring bar, and stirrer was prepared using the following formula (A) obtained in Synthesis Example 2 above. The monomer represented by (general formula (I-1)) has a number-average molecular weight of Rf: approximately 1,450, and a terminal group (acryloyloxy group) concentration of 6.24 × 10⁻¹⁴. -4 mol / g, molecular weight: approximately 1622.16) 19.64 g (compound mol amount: 1.23 x 10 -2 mol, polymerizable group mol amount: 1.23×10 -2 mol), trimethylolpropane triacrylate (molecular weight: 296.32) 0.363 g (mol amount of compound: 1.23 × 10⁻¹⁶) -3 mol, polymerizable group mol amount: 3.68×10 -3 mol), 15.0 g of m-xylene hexafluoride as a solvent, 15.0 g of Novec 7300 (manufactured by 3M Co., Ltd.), and 0.100 g of V-59 (2,2'-azobis(2-methylbutyronitrile)) as a radical polymerization initiator (5.20 x 10) -4 A mol (unit) was added and reacted at 65°C for 20 hours while aeration with nitrogen gas. Then, Novec 7300 was added to achieve an active ingredient concentration of 15% by mass, and a coating solution of a copolymer of the monomer represented by formula (A) and trimethylolpropane triacrylate was prepared. The kinematic viscosity of the resulting copolymer was 6.83 mm. 2 It was / s.

[0087] [Example 4] Into a 100 mL four-necked flask equipped with a thermometer, a nitrogen gas inlet, a reflux condenser, a stirring bar and a stirrer, the following formula (A) obtained in Synthesis Example 2 above The monomer represented by (the number average molecular weight of Rf in general formula (I-1): equivalent to about 1,450, terminal group (acryloyloxy group) concentration: 6.24×10 -4 mol / g, molecular weight: about 1622.16) 19.85 g (compound molar amount: 1.24×10 -2 mol, polymerizable group molar amount: 1.24×10 -2 mol), the following formula (b-2) 0.295 g of a 50 mass% m-xylene hexafluoride solution of Compound (B) (molecular weight: 397.38) containing the compound represented by as the main component (compound molar amount: 3.71×10 -4 mol, polymerizable group molar amount: 1.11×10 -3 mol), 1.85 g of m-xylene hexafluoride as a solvent, 28.0 g of Novec 7300 (manufactured by 3M Company) and 0.100 g (5.20×10 -4 mol) of V-59 (2,2'-azobis(2-methylbutyronitrile)) as a radical polymerization initiator were charged, and the reaction was carried out at 65°C for 20 hours while passing nitrogen gas therethrough. Thereafter, Novec 7300 was added so that the active ingredient concentration was 15 mass%, to prepare a coating liquid of a copolymer of the monomer represented by formula (A) and Compound (B) containing the compound represented by formula (b-2) as the main component. The kinematic viscosity of the obtained copolymer solution was 11.1 mm 2 / s.

[0088] [Example 5] Into a 100 mL four-necked flask equipped with a thermometer, a nitrogen gas inlet, a reflux condenser, a stirring bar and a stirrer, the following formula (A) obtained in Synthesis Example 2 above The monomer represented by (the number average molecular weight of Rf in general formula (I-1): equivalent to about 1,450, terminal group (acryloyloxy group) concentration: 6.24×10 -4 mol / g, molecular weight: about 1622.16) 19.39 g (compound molar amount: 1.21×10 -2 mol, polymerizable group molar amount: 1.21×10 -2mol), tris(2-acryloyloxyethyl) isocyanurate (molecular weight: 423.38) 0.615 g (compound molar amount: 1.45×10 -3 mol, polymerizable group molar amount: 4.35×10 -3 mol), 15.0 g of m-xylene hexafluoride as a solvent, 15.0 g of Novec 7300 (manufactured by 3M Company) and 0.100 g (5.20×10 -4 mol) of V-59 (2,2'-azobis(2-methylbutyronitrile)) as a radical polymerization initiator were charged, and the mixture was reacted at 65°C for 20 hours while introducing nitrogen gas. Thereafter, Novec 7300 was added so that the active ingredient concentration was 15 mass%, to prepare a coating liquid of a copolymer of the monomer represented by formula (A) and tris(2-acryloyloxyethyl) isocyanurate. The kinematic viscosity of the resulting copolymer solution was 10.5 mm 2 / s.

[0089] [Comparative Example 1] Into a 100 mL four-necked flask equipped with a thermometer, a nitrogen gas inlet, a reflux condenser, a stirrer bar and a stirrer, the following formula (A) obtained in the above Synthesis Example 2 The monomer represented by (the number average molecular weight of Rf in the general formula (I-1): equivalent to about 1,450, terminal group (acryloyloxy group) concentration: 6.24×10 -4 mol / g, molecular weight: about 1622.16) 20.00 g (compound molar amount: 1.25×10 -2 mol, polymerizable group molar amount: 1.25×10 -2 mol), 30.0 g of Novec 7300 (manufactured by 3M Company) as a solvent and 0.100 g (5.20×10 -4 mol) of V-59 (2,2'-azobis(2-methylbutyronitrile)) as a radical polymerization initiator were charged, and the mixture was reacted at 65°C for 20 hours while introducing nitrogen gas. Thereafter, Novec 7300 was added so that the active ingredient concentration was 15 mass%, to prepare a coating liquid of a polymer of the monomer represented by formula (A). The kinematic viscosity of the resulting polymer solution was 24.2 mm 2 / s.

[0090] [Comparative Example 2] A 100 mL four-necked flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, stirring bar, and stirrer was prepared using the following formula (A) obtained in Synthesis Example 2 above. The monomer represented by (general formula (I-1)) has a number-average molecular weight of Rf: approximately 1,450, and a terminal group (acryloyloxy group) concentration of 6.24 × 10⁻¹⁴. -4 mol / g, molecular weight: approximately 1622.16) 19.74 g (compound mol amount: 1.23 x 10 -2 mol, polymerizable group mol amount: 1.23×10 -2 mol), the following formula (c-3) A compound whose main component is the compound represented by (number average molecular weight of fluoropolyether group: approximately 5,810, terminal group (acryloyloxy group) concentration: 2.92 × 10 -4 mol / g, molecular weight: approximately 6268.42) 0.262 g (compound mol amount: 3.83 x 10 -5 mol, polymerizable group mol amount: 7.65×10 -5 mol), 15.0 g of m-xylene hexafluoride as a solvent, 15.0 g of Novec 7300 (manufactured by 3M Co., Ltd.), and 0.100 g of V-59 (2,2'-azobis(2-methylbutyronitrile)) as a radical polymerization initiator (5.20 x 10) -4 A mol (unit) was added and reacted at 65°C for 20 hours while aeration with nitrogen gas. Then, Novec 7300 was added to achieve an active ingredient concentration of 15% by mass, and a coating solution of a copolymer of the monomer represented by formula (A) and the compound represented by formula (c-3) was prepared. The kinematic viscosity of the resulting copolymer was 19.5 mm. ２ It was / s.

[0091] [Comparative Example 3] A 100 mL four-necked flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, stirring bar, and stirrer was prepared using the following formula (A) obtained in Synthesis Example 2 above. The monomer represented by (general formula (I-1)) has a number-average molecular weight of Rf: approximately 1,450, and a terminal group (acryloyloxy group) concentration of 6.24 × 10⁻¹⁴. -4 mol / g, molecular weight: approximately 1622.16) 19.32 g (compound mol amount: 1.21 x 10 -2mol, polymerizable group mol amount: 1.21×10 -2 mol), EBECRYL8701 (manufactured by Daicel Ornex Co., Ltd., terminal group concentration: 1.5 × 10) -3 mol / g, molecular weight: approximately 2000.00) 0.680 g (compound mol amount: 3.40 x 10 -4 mol, polymerizable group mol amount: 1.02×10 -3 mol), 15.0 g of m-xylene hexafluoride as a solvent, 15.0 g of Novec 7300 (manufactured by 3M Co., Ltd.), and 0.100 g of V-59 (2,2'-azobis(2-methylbutyronitrile)) as a radical polymerization initiator (5.20 x 10) -4 A mol (unit) was added and reacted at 65°C for 20 hours while aeration with nitrogen gas was performed. Then, Novec 7300 was added to achieve an active ingredient concentration of 15% by mass, and a coating solution of a copolymer of the monomer represented by formula (A) and EBECRYL 8701 was prepared. The kinematic viscosity of the resulting copolymer was 6.60 mm. ２ It was / s.

[0092] <Preparation of glass samples for contact angle measurement> The coating solutions prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were dip-coated onto glass slides (S1127, 76 mm x 26 mm, manufactured by Matsunami Glass Industry Co., Ltd.) under the following conditions to prepare glass samples with a coating thickness of 1.0 to 3.0 μm. [Dip coating conditions] Coating equipment: Tabletop dip coater (DT-0303-S3, manufactured by SDI Corporation) Immersion time: 30 seconds Withdrawal speed: 0.3 mm / second Drying after coating: Room temperature, 30 minutes

[0093] [Water Contact Angle, Hexadecane (HD) Contact Angle] The contact angles (water repellency and oil repellency) of the glass samples prepared above for contact angle measurement were measured using a Drop Master contact angle meter (DMo-701SA, manufactured by Kyowa Interface Science Co., Ltd.) to water and hexadecane (HD) (droplet: 2 μL, temperature: 25°C, relative humidity: 40%). The measurement was performed by taking a picture of the pure water 3 seconds after dropping or the hexadecane 1 second after dropping with a CCD camera connected to the contact angle meter, and then analyzing the droplet image with the FAMAS contact angle analysis software attached to the above contact angle measuring instrument to measure the contact angle between the glass substrate and the droplet. The contact angle was calculated using the θ / 2 method. The analysis conditions and evaluation criteria are as follows. The results (initial water contact angle or initial HD contact angle) are shown in Table 2. Initially, both the example and comparative example showed good water repellency. [Analysis Conditions] Method: Droplet method (θ / 2 method) Droplet recognition: Automatic Droplet recognition line (distance from needle tip): 50 dots Algorithm: Automatic Image mode: Frame threshold level: Automatic [Evaluation Criteria] Pure water contact angle A: 125° or more B: 115° or more, less than 125° C: Less than 115° HD contact angle A: 75° or more B: 65° or more, less than 75° C: Less than 65°

[0094] <Preparation of PTFE Samples> To the coating solutions prepared in Examples 1-5 and Comparative Examples 1-3, a fluorine-based solvent (Novec 7300 / m-hexafluoroxylene = 7:3 (parts by mass)) was added to prepare a diluted solution so that the active ingredient concentration was 3% by mass. Subsequently, PTFE (polytetrafluoroethylene) porous membranes (PF-100, manufactured by ADVANTEC) cut to 70 mm x 26 mm were dip coated under the following conditions to prepare PTFE samples with a coating amount of 8.0-11.0% by mass. [Dip Coating Conditions] Coating equipment: Tabletop dip coater (DT-0303-S3, manufactured by SDI Corporation) Immersion time: 30 seconds Pull-out speed: 3.0 mm / second Drying after coating: Room temperature, 30 minutes

[0095] [Initial Oil Repellency] Initial oil repellency was evaluated according to AATCC Test Method 118-2020. One drop of the test solution shown in Table 1 was added to the PTFE sample obtained above using a Pasteur pipette. After 30 seconds, if the droplet did not penetrate, the test solution was considered acceptable. The highest grade of the acceptable test solution was defined as the oil repellency. The results are shown in Table 2.

[0096]

[0097] [Heat Resistance of PTFE Coating Film (Oil Repellency After Heat Resistance)] The PTFE samples whose initial oil repellency was evaluated above were left at 150°C for 100 hours. Subsequently, the oil repellency after the heat resistance test was measured according to AATCC Test Method 118-2020, and the heat resistance (oil repellency after heat resistance) of the PTFE coating film was evaluated based on the following criteria. The results are shown in Table 2. [Evaluation Criteria] A: [Initial oil repellency] - [Oil repellency after heat resistance test] = Grade 0 B: [Initial oil repellency] - [Oil repellency after heat resistance test] = Grade 1 C: [Initial oil repellency] - [Oil repellency after heat resistance test] ≥ Grade 2

[0098] [Reproducibility of Degree of Polymerization] Synthesis was performed four times for each of Examples 1-5 and Comparative Examples 1-3 in the same manner as the formulations described, and the kinematic viscosity of the copolymer solution or polymer solution (15% by mass) was measured. The coefficient of variation (CV) of the obtained kinematic viscosity values ​​was calculated, and the reproducibility of the degree of polymerization was evaluated based on the following criteria. The results are shown in Table 2. Coefficient of variation (CV) (%) = [Standard deviation of kinematic viscosity (mm)] 2 / s)] / [Average dissolution kinematic viscosity (mm 2 / s)] × 100 [Evaluation Criteria] A: Coefficient of variation (CV) is less than 35% B: Coefficient of variation (CV) is 35% or more and less than 50% C: Coefficient of variation (CV) is 50% or more D: Some gels formed, making accurate calculation impossible E: Some polymerized at all, making calculation impossible In the four synthesis tests, some comparative examples formed gels, and some comparative examples did not polymerize at all.

[0099] <Preparation of glass samples for heat resistance measurement> For each coating solution synthesized four times in the same manner as described in Examples 1 to 5 and Comparative Examples 1 to 3, a fluorine-based solvent (Novec 7300 / m-hexafluoroxylene = 7:3 (parts by mass)) was added to prepare a diluent so that the active ingredient concentration was 3% by mass. The prepared diluent was dipped onto a glass slide (Matsunami Glass Industry Co., Ltd., S1127, 76 mm x 26 mm) under the following conditions to prepare glass samples with a coating thickness of 0.05 to 0.3 μm. [Dip coating conditions] Coating equipment: Tabletop dip coater (SDI Corporation, DT-0303-S3) Immersion time: 30 seconds Pull-out speed: 0.3 mm / second Drying after coating: Room temperature, 30 minutes Note that for the coating solution of Comparative Example 3 that did not polymerize, a coating film could not be formed and repulsion occurred. For the other coating films, no repellency was observed in any of the samples. Here, repellency in a coating film refers to a condition where holes are created in the coating film, exposing the substrate surface.

[0100] [Heat Resistance of Glass Coating Films (Presence or Absence of Repulsion)] For the four glass samples prepared above for heat resistance measurement, the coating film surface was observed before and after heating using a 3D measuring laser microscope (Olympus Corporation, LEXT OLS4100) with a standard objective lens: MPFLN5X (magnification: 5x). Heat resistance was evaluated based on the presence or absence of repulsion on the coating film surface after heating. The heating conditions were 125±2℃ for 24 hours in accordance with JIS K5600-6-3, and the heat resistance of the glass coating film (presence or absence of repulsion) was evaluated based on the following criteria. The results are shown in Table 2. [Evaluation Criteria] A: None of the four coating films showed repulsion after heating. B: Only one coating film showed repulsion after heating. C: Two or more coating films showed repulsion after heating. D: Accurate observation of the film surface was impossible after heating due to the presence of gel. E: Some samples failed to form a coating film, and among the samples that did form a coating film, some were rejected.

[0101] [Presence or absence of PFOA, PFHxA and related substances] The monomers in the coating solutions prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated as follows: those that did not contain PFOA (perfluorooctanoic acid), which has been pointed out as accumulating in the human body and the environment, and PFHxA (perfluorohexanoic acid), which is of similar risk, and related substances were evaluated as A; those that contained PFOA, PFHxA, and related substances were evaluated as C. The results are shown in Table 2.

[0102]

[0103] Examples 1 to 5 all exhibited excellent initial water contact angle, initial HD contact angle, initial oil repellency, and PTFE coating film heat resistance (oil repellency after heat resistance). The copolymer of the present invention, even when containing monomers that do not contain fluorine atoms as monomer components, obtained properties (initial water contact angle, initial HD contact angle, initial oil repellency, PTFE coating film heat resistance (oil repellency after heat resistance)) comparable to those of Comparative Example 1, a polymer that does not contain monomers that do contain fluorine atoms and whose monomer components consist only of monomers that do contain fluorine atoms, and was therefore suitable for practical use. Furthermore, Examples 1 to 5 exhibited excellent reproducibility of the degree of polymerization and excellent heat resistance of the glass coating film (presence or absence of water repellency). In contrast, Comparative Examples 1 to 3, which did not contain monomer (II), showed poor reproducibility of the degree of polymerization and poor heat resistance of the glass coating film (presence or absence of water repellency).

Claims

1. A copolymer comprising (I) a fluorine-containing monomer having a monovalent fluoropolyether group and a polymerizable group at its terminus, wherein the fluoropolyether group and the polymerizable group are bonded directly or via a linker, and (II) a monomer having at least one polymerizable group and having a molecular weight smaller than that of the fluorine-containing monomer (I), as a monomer component.

2. The copolymer according to claim 1, wherein the number average molecular weight of the monovalent fluoropolyether groups in the fluorine-containing monomer (I) is 1,000 to 5,000.

3. The copolymer according to claim 1, wherein the molecular weight of monomer (II) is less than 1,000.

4. The copolymer according to claim 1, wherein monomer (II) does not contain a fluorine atom.

5. The copolymer according to claim 1, wherein the monovalent fluoropolyether group in the fluorine-containing monomer (I) is a monovalent fluoropolyether group whose terminal is sealed with a fluoroalkyl group having 5 or fewer carbon atoms.

6. The copolymer according to claim 1, wherein the monovalent fluoropolyether group in the fluorine-containing monomer (I) is represented by the following average formula (1). (In the formula, k is an integer between 0 and 4, m is an integer between 1 and 5 independently for each unit, n is a positive number between 3 and 73, and p is an integer between 1 and 3. Each of these units may be linear or branched.) 7. The copolymer according to claim 1, wherein the polymerizable group in the fluorine-containing monomer (I) is a group selected from a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)allyl group, a vinyl group, a vinylene group, and a vinylidene group.

8. The copolymer according to claim 1, wherein the linker in the fluorine-containing monomer (I) is an unsubstituted or substituted divalent or greater hydrocarbon group which may contain one or more selected from an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond.

9. The copolymer according to claim 1, wherein the fluorine-containing monomer (I) is a fluorine-containing monomer represented by the following general formula (I-1). (In the formula, Rf is a monovalent fluoropolyether group with a number-average molecular weight of 1,000 to 5,000, terminated by a perfluoroalkyl group having 5 or fewer carbon atoms; X is an unsubstituted or substituted divalent hydrocarbon group which may contain a single bond or one or more selected from an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond; and R is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group.) 10. The copolymer according to claim 9, wherein Rf in general formula (I-1) is represented by the following average formula (1). (In the formula, k is an integer between 0 and 4, m is an integer between 1 and 5 independently for each unit, n is a positive number between 3 and 73, and p is an integer between 1 and 3. Each of these units may be linear or branched.) 11. The copolymer according to claim 9, wherein X in general formula (I-1) is selected from a single bond, an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, and a structure represented by the following general formulas (2) to (7). (In the formula, the parts indicated by * are the bonding sites with the oxygen atom in general formula (I-1), and the parts indicated by ** are the bonding sites with Rf in general formula (I-1).) 12. The copolymer according to claim 9, wherein R in general formula (I-1) is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, or a phenyl group.

13. The monomer (II) is a 2- to 4-valent unsubstituted or substituted saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an ether bond, a carbonyl bond, an ester bond, -NR 1 - bond, -C(=O)NR 1 - bond, -OC(=O)NR 1 - bond, -NR 1 C(=O)NR 2 - bond, -NR 1 C(=O)N= bond, -C(=O)NR 1 C(=O)- bond (R 1 , R 2 each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms), a cyclopentane ring, a cyclohexane ring, a benzene ring, and a nitrogen-containing 5-membered ring or nitrogen-containing 6-membered ring containing one or more nitrogen atoms in the ring structure (these ring structures may contain a carbonyl bond, and hydrogen atoms in the ring structure may be substituted by an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, or an NH₂ group), the monomer having a 1- to 6-valent structure of one or a combination of two or more selected from the group consisting of the foregoing in the molecule, and having a polymerizable unsaturated ethylene group, the copolymer according to claim 1.

14. The copolymer according to claim 1, wherein monomer (II) is copolymerized in a proportion of 0.1 to 5% by mass relative to the total mass of monomer (I) and monomer (II).

15. The copolymer according to claim 1, wherein the coefficient of variation (CV) of the kinematic viscosity of 15% by mass solvent dissolution in four synthesis lots synthesized under the same conditions is less than 50%.

16. A water-repellent and oil-repellent agent containing the copolymer according to any one of claims 1 to 15.

17. The water-repellent and oil-repellent agent according to claim 16, which provides a coating on a glass plate with a water contact angle of 115° or more.

18. The water-repellent and oil-repellent agent according to claim 16, which provides a coating on a glass plate in which the hexadecane contact angle is 65° or more.

19. The water- and oil-repellent agent according to claim 16, which provides a film in which the oil repellency, when applied to a substrate, is grade 7 or higher according to the AATCC test method 118-2020, and in which the oil repellency does not decrease from the initial oil repellency after heating at 150°C for 100 hours.

20. An article having a water-repellent and oil-repellent coating on its surface as described in claim 16.

21. The article according to claim 20, wherein the article is a fiber or a porous membrane.

22. The article according to claim 21, wherein the fibers or porous membrane are composed of fluororesin.

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