Water and oil repellent agent, and article

Abstract

A water and oil repellent agent containing a polymer of a monomer represented by general formula (I) (in the formula, R is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; X is a single bond or an unsubstituted or substituted divalent hydrocarbon group that may contain one or more options selected from among an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond; and Rf is a monovalent fluoropolyether group that has terminals capped by perfluoroalkyl groups having 5 or less carbon atoms, and that has a number average molecular weight of 1,000 to 5,000) maintains good water and oil repellency not only at an initial stage but also under heat-resistant conditions.

Description

Water and oil repellents and articles

[0001] The present invention relates to a water / oil repellent agent and an article containing a fluorine-containing polymer as an active ingredient. More specifically, the present invention relates to a water / oil repellent agent containing a polymer of an acrylic monomer containing a fluoropolyether group as an active ingredient, and an article having a coating of the water / oil repellent on its surface.

[0002] Conventionally, in order to provide a surface modification function such as water-repellent and oil-repellent properties to a substrate, a polymer of a fluorine-containing acrylic or methacrylic monomer has been applied to the substrate, as shown in Patent Document 1 (JP-B 1-42983) and Patent Document 2 (JP-A 7-109317).

[0003] Long-chain perfluoroalkyl groups with eight or more carbon atoms have been used to achieve surface modification functions such as high water and oil repellency. However, it has been pointed out that long-chain perfluorocarboxylic acids with perfluoroalkyl groups with eight or more carbon atoms, such as perfluorooctanoic acid (PFOA), have the potential to accumulate in the human body.

[0004] In order to reduce the risk to living organisms and the environment, PFOA has been replaced with, for example, perfluorohexanoic acid (PFHxA), which has 6 carbon atoms. For example, Patent Document 3 (JP 2020-50757 A) discloses a surface modifier containing, as an active ingredient, a polymer of a (meth)acrylic acid derivative containing a perfluoroalkyl group having 6 carbon atoms.

[0005] However, similar risks remain a concern for PFHxA.

[0006] Japanese Patent Publication No. 1-42983 Publication No. 7-109317 Publication No. 2020-50757

[0007] The present invention has been made in view of the above circumstances, and aims to provide a water / oil repellent agent that exhibits good water / oil repellency not only initially but also under heat-resistant conditions, despite the perfluoroalkyl group having less than 6 carbon atoms (5 or less), and an article having a coating of the water / oil repellent agent on its surface.

[0008] As a result of intensive research conducted by the present inventors to achieve the above object, they discovered that a water / oil repellent agent containing a polymer obtained by polymerizing an acrylate ester-based monomer having a specific linker structure and having monovalent fluoropolyether groups with a number average molecular weight of 1,000 to 5,000, the terminals of which are blocked with perfluoroalkyl groups having 5 or less carbon atoms, maintains good water / oil repellency not only initially but also under heat-resistant conditions, thereby completing the present invention.

[0009] Therefore, the present invention provides the following water and oil repellent and article: [1] A water repellent and an article comprising a compound represented by the following general formula (I): (wherein R is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; X is a single bond, or an unsubstituted or substituted divalent hydrocarbon group which may contain one or more bonds selected from an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond; and Rf is a monovalent fluoropolyether group which is end-capped with a perfluoroalkyl group having 5 or less carbon atoms and has a number average molecular weight of 1,000 to 5,000). [2] The water and oil repellent according to [1], wherein R in general formula (I) is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, or a phenyl group. [3] The water and oil repellent according to [1] or [2], wherein X in general formula (I) is any one selected from a single bond, an unsubstituted or substituted alkylene group having 1 to 15 carbon atoms which may contain an oxygen atom, and a structure represented by the following general formula (1) or (2): (The position indicated by * in each of formulas (1) and (2) is the bonding position to the carbon atom in general formula (I), and the position indicated by ** is the bonding position to the Rf group in general formula (I).) [4] The water / oil repellent according to any one of [1] to [3], wherein the Rf group in general formula (I) is represented by the following general formula (3) or (4): (In the formula, n is an integer from 5 to 28.) (In the formula, p is an integer of 0 to 41, q is an integer of 0 to 73, and is a number that satisfies p+q=8 to 73. Each repeating unit shown in parentheses followed by p and q may be bonded randomly. The position shown by ** in each formula is the bonding position to X in general formula (I).) [5] The water / oil repellent according to any one of [1] to [4], which, when applied to a glass plate, provides a coating having a water contact angle of 115° or more. [6] The water / oil repellent according to any one of [1] to [5], which, when applied to a glass plate, provides a coating having a hexadecane contact angle of 75° or more. [7] The water / oil repellent according to any one of [1] to [6], which, when applied to a substrate, provides a coating having an oil repellency of grade 7 or higher according to AATCC test method 118-2020, and whose oil repellency does not decrease from the initial oil repellency after heating at 150°C for 100 hours. [8] The water / oil repellent according to [7], wherein the substrate to be coated is a fiber or a porous membrane. [9] The water / oil repellent according to [8], wherein the porous membrane is made of PTFE (polytetrafluoroethylene).

[10] An article having a surface coated with the water / oil repellent according to any one of [1] to [9].

[0010] According to the water / oil repellent of the present invention, it is possible to provide a water / oil repellent that exhibits good water / oil repellency not only initially but also under heat-resistant conditions, even though the number of carbon atoms in the perfluoroalkyl group moiety of the monomer that forms the contained polymer is less than 6 (5 or less), and to provide an article having a coating of the water / oil repellent on its surface.

[0011] The water / oil repellent of the present invention contains a polymer of a monomer represented by the following general formula (I). (In the formula, R represents a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; X represents a single bond, or an unsubstituted or substituted divalent hydrocarbon group which may contain one or more bonds selected from the group consisting of an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond; and Rf represents a monovalent fluoropolyether group whose terminals are capped with perfluoroalkyl groups having 5 or less carbon atoms and which has a number average molecular weight of 1,000 to 5,000.)

[0012] In the general formula (I), R is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and examples of the halogen atom, alkyl group, or aryl group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, and a phenyl group. R is preferably a hydrogen atom or a methyl group.

[0013] In the general formula (I), X is a single bond, or an unsubstituted or substituted divalent hydrocarbon group which may contain one or more bonds selected from the group consisting of an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond, and is part of a linking group (linker) between the Rf group and the acrylate ester terminal. The linking group is characterized in that the X group is bonded to the Rf group, the X group is bonded to the oxygen atom of the urethane bond via a methylene group, and the nitrogen atom of the urethane bond is bonded to the oxygen atom of the acrylate ester terminal via an ethylene group. Examples of unsubstituted or substituted divalent hydrocarbon groups which may contain one or more bonds selected from oxygen atoms, amino bonds, amide bonds, urethane bonds, and urea bonds include alkylene groups such as methylene groups, ethylene groups, propylene groups (trimethylene groups, methylethylene groups), butylene groups (tetramethylene groups, methylpropylene groups), hexamethylene groups, and octamethylene groups, arylene groups such as phenylene groups, and combinations of two or more of these groups (alkylene-arylene groups, etc.). The divalent hydrocarbon group having 1 to 15 carbon atoms may contain one or more bonds selected from an ether bond (-O-(oxygen atom)), an amino bond (-NH-), an amide bond (-C(=O)NH-), a urethane bond (-OC(=O)NH-) and a urea bond (-NHC(=O)NH-), or may be a substituted divalent hydrocarbon group in which some or all of the hydrogen atoms bonded to carbon atoms have been substituted with halogen atoms such as fluorine or iodine. The divalent hydrocarbon group having 1 to 15 carbon atoms may contain a bond in which two amide bonds are repeated.

[0014] X is preferably a single bond, an unsubstituted or substituted alkylene group having 1 to 15 carbon atoms which may contain an oxygen atom, or a structure represented by the following general formula (1) or (2). (In each of formulas (1) and (2), the position indicated by * is the bonding position to the carbon atom in general formula (I), and the position indicated by ** is the bonding position to the Rf group in general formula (I).)

[0015] In the general formula (I), Rf is a monovalent fluoropolyether group whose terminals are capped with perfluoroalkyl groups having 5 or less carbon atoms and whose number average molecular weight is 1,000 to 5,000, preferably a monovalent perfluoropolyether group whose number average molecular weight is 1,000 to 5,000, and more preferably a monovalent perfluoropolyether group containing a repeating unit represented by the following general formula (5): (In the formula, a is a positive number from 0 to 28, b is a positive number from 0 to 41, and c is a positive number from 0 to 73, and the numbers satisfy the relationship a+b+c=5 to 73. The repeating units shown in parentheses with a, b, and c may be bonded randomly.)

[0016] Examples of the repeating unit represented by the general formula (5) include units represented by the following formulas:

[0017] Among these, the repeating units represented by the following formula are particularly preferred.

[0018] Rf (monovalent fluoropolyether group) is a perfluoroalkyl group having 5 or less carbon atoms at the end, such as CF3-, C2F5-(CF3CF2-), C3F7-(CF3CF2CF2-, (CF3)2CF-), C4F9-(CF3(CF2)3-), C5F 11 -(CF3(CF2)4-) and the like.

[0019] In the present invention, preferred Rf groups are those having structures represented by the following general formulas (3) and (4). (In the formula, n is an integer from 5 to 28.) (In the formulae, p is an integer of 0 to 41, and q is an integer of 0 to 73, and the numbers satisfy p+q=8 to 73. The repeating units shown in parentheses with p and q may be bonded randomly. In each formula, the position indicated by ** is the bonding position to X in general formula (I).)

[0020] The Rf group is more preferably a structure represented by the following general formula (6). (In the formula, the position indicated by ** is the bonding position to X in the general formula (I).)

[0021] In the present invention, the number average molecular weight of the Rf group portion is 1,000 to 5,000, preferably 1,300 to 4,200. If the number average molecular weight of the Rf group portion is less than 1,000, the heat resistance of the coating (water and oil repellency after a heat resistance test) will be poor, and if it exceeds 5,000, the viscosity will be high, making it difficult to handle during polymerization, and the initial water and oil repellency and heat resistance (water and oil repellency after a heat resistance test) of the coating will be poor. In the present invention, the number average molecular weight of the Rf group portion is, for example, 19 It can be determined by F-NMR or the like.

[0022] Examples of the monomer represented by the above general formula (I) include those represented by the following formula: (wherein n, p, and q are the same as above.)

[0023] The monomer represented by the general formula (I) can be prepared, for example, by reducing a fluoropolyether compound having a C(═O)F group or a carboxy group at one end to a fluoropolyether compound having a hydroxy group at one end, followed by reaction with an isocyanate compound having an acryloyl or methacryloyl group. The fluoropolyether compound having a C(═O)F group or a carboxy group at one end can be aged together with a solvent such as tetrahydrofuran and a reducing agent such as a toluene solution of bis(2-methoxyethoxy)aluminum sodium 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 hydroxy group at one end. The resulting fluoropolyether compound having a hydroxy group at one end is mixed with 2-isocyanatoethyl acrylate and a polymerization inhibitor such as 4-methoxyphenol, and the mixture is heated at a temperature of 25 to 55°C, preferably 40 to 50°C, followed by the addition of a catalyst such as tetrakis(2-ethylhexyl) orthotitanate and aging for 2 to 24 hours, thereby obtaining the monomer represented by the above general formula (I). 2-isocyanatoethyl methacrylate may be used instead of 2-isocyanatoethyl acrylate.

[0024] The polymer according to the present invention can be obtained by polymerizing the monomer represented by the formula (I) dissolved in a solvent using a radical polymerization initiator by a known method such as solution polymerization.

[0025] The solvent used in the method for producing a polymer according to the present invention is not particularly limited as long as it can dissolve the monomer represented by formula (I), but a fluorine-based solvent is preferred. Examples of fluorine-based solvents include Novec 7300, Novec 7200, and Novec 7100 (manufactured by 3M), AC-6000 and AE-3000 (manufactured by AGC Inc.), hexafluoroacetone, hexafluoroisopropanol, and m-xylene hexafluoride (manufactured by Central Glass Co., Ltd.). Among these, Novec 7300 is preferred from the viewpoint of solubility. The amount of solvent used is not particularly limited, but is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass, and even more preferably 150 to 400 parts by mass, per 100 parts by mass of the monomer represented by formula (I).

[0026] Examples of radical polymerization initiators that can be used in the method for producing a polymer according to the present invention include dimethyl azobisisobutyrate (V-601), cumene hydroperoxide, succinic acid 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-methylamidoxime) dihydrochloride, 2,2'-azobis(2-methylbutyronitrile) (V-59), 2,2'-azobis(isobutylamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazoline-2-yl)-2-methylpropional], ) propane] and its disulfate, 2,2'-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-cumyl peroxide, t-butyl peroxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxyisopropyl carbonate, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)-p-diisopropylbenzene, and other azo compounds and organic peroxides, potassium persulfate, sodium persulfate, and ammonium persulfate. These radical polymerization initiators may be used alone or in combination of two or more. The amount of the radical polymerization initiator used is not particularly limited, but is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the monomer represented by formula (I).

[0027] In the polymerization method using the solvent and the radical polymerization initiator, the polymerization conditions for the monomer represented by formula (I) are preferably an inert gas atmosphere at 40 to 120°C, particularly 65 to 70°C, for 4 to 30 hours, particularly 18 to 24 hours.

[0028] The polymer of the monomer represented by formula (I) thus obtained has a 15% by mass solvent solution kinematic viscosity of 1 to 150 mm 2 / s, and 5 to 80 mm 2 / s is more preferable. If the solution kinematic viscosity is too low, the surface properties may be poor when applied to a substrate, while if it is too high, workability during application may be poor. The solution kinematic viscosity can be measured using a Cannon-Fenske viscometer according to the method described in JIS Z8803:2011. The solvent is not particularly limited as long as it can dissolve the polymer of the monomer represented by formula (I), 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), AC-6000, AE-3000 (manufactured by AGC Inc.), hexafluoroacetone, hexafluoroisopropanol, and m-xylene hexafluoride (manufactured by Central Glass Co., Ltd.). Among these, Novec 7300 is preferable from the viewpoint of solubility.

[0029] The water / oil repellent of the present invention contains a polymer of the monomer represented by formula (I) described above. The water / oil repellent of the present invention is usually provided as a solvent solution of the polymer. The amount of polymer in the solvent solution (polymer concentration) is desirably 1 to 50% by mass, particularly 3 to 30% by mass, and even more preferably 3 to 15% by mass.

[0030] The solvent used for the water / oil repellent agent is not particularly limited as long as it can dissolve the polymer of the monomer, but a fluorine-based solvent is preferred. Examples of fluorine-based solvents include Novec 7300, Novec 7200, and Novec 7100 (manufactured by 3M), AC-6000 and AE-3000 (manufactured by AGC Inc.), hexafluoroacetone, hexafluoroisopropanol, and m-xylene hexafluoride (manufactured by Central Glass Co., Ltd.). Among these, Novec 7300 is desirable from the viewpoint of solubility. The solvent used in the method for producing the polymer may be used as is for the water / oil repellent agent, or the solvent may be further added after the production of the polymer to adjust the concentration of the polymer.

[0031] The water / oil repellent of the present invention can be applied to a substrate by, for example, spin coating, dip coating, spraying, roll coating, meniscus coating, or screen printing.

[0032] The water- and oil-repellent agent of the present invention can easily form a coating on a substrate surface by applying it to the substrate, such as glass, fiber, or porous membrane, and then drying the solvent. Specifically, drying is preferably carried out at room temperature (25°C ± 10°C) for 30 minutes to 24 hours. To speed up drying, the agent may be heated, for example, at 40 to 150°C for 30 seconds to 24 hours, within a range that does not affect the substrate. This coating exhibits excellent water- and oil-repellent properties due to the inclusion of fluorine atoms in the polymer. Therefore, it can be used as a water- and oil-repellent coating agent for glass, fiber, porous membranes, and the like, particularly fiber and porous membranes.

[0033] The fibrous substrate to which the water / oil repellent of the present invention is applied may be in the form of, for example, fiber, thread, cloth, etc. Examples of fibers constituting the fibrous substrate include glass fiber, carbon fiber, aramid fiber, polyethylene fiber, polytetrafluoroethylene (PTFE) fiber, Zylon fiber, boron fiber, basalt fiber, metal fiber, polyamide fiber, silicon carbide fiber, polyester fiber, ceramic fiber, alumina fiber, mineral fiber, rock fiber, slag fiber, polyoxymethylene fiber, aromatic polyamide fiber, polyparaphenylene benzobisoxazole fiber, plant fiber, cellulose fiber, and lignin fiber. These fibers may be used alone or in combination of two or more.

[0034] Examples of the porous membrane substrate to which the water / oil repellent of the present invention is applied include nonwoven fabric, perforated membrane, microporous membrane, porous body, etc. Materials constituting the porous membrane substrate include resins such as PTFE (polytetrafluoroethylene), ceramics, metals, etc., and preferably PTFE (polytetrafluoroethylene).

[0035] The thickness of the coating is selected appropriately depending on the type of substrate, but is usually 0.01 to 50 μm, particularly 0.1 to 10 μm. The thickness of the coating can be calculated, for example, by the following formula: [Coating thickness (μm)] = [Increase in substrate mass (g) before and after coating] ÷ [Density of water / oil repellent agent (g / cm 3 )]÷[Substrate area (cm 2 ) ÷ 2 × 10,000

[0036] The film thickness can also be measured by means of spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry, X-ray fluorescence measurement, or the like.

[0037] Examples of articles having a coating of the water / oil repellent of the present invention on their surface include in-vehicle products, textile products, nonwoven fabrics, and filtering materials used in the presence of organic solvent liquids or their vapors.

[0038] The water / oil repellent of the present invention is applied to a glass plate to form a coating, and the coating has a contact angle with water (water contact angle) of 115° or more, preferably 120° or more at a temperature of 25° C. and a relative humidity of 40%. In the present invention, the water contact angle is a value measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) under the condition of a 2 μL droplet.

[0039] Furthermore, it is preferable that the contact angle of a coating formed by applying the water / oil repellent of the present invention to a glass plate with hexadecane (hexadecane (HD) contact angle) at a temperature of 25°C and a relative humidity of 40% is 75° or more, preferably 78° or more. In the present invention, the contact angle with hexadecane is a value measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) under the condition of a droplet size of 2 μL.

[0040] Furthermore, it is preferable that the coating formed using the water and oil repellent agent of the present invention has an oil repellency of grade 7 or higher according to AATCC test method 118-2020, and that the oil repellency after heating at 150°C for 100 hours does not decrease from the initial oil repellency.

[0041] The present invention will be specifically explained below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the synthesis examples and examples below. In the following examples, the number average molecular weight of the fluoropolyether group (Rf in general formula (I)) is 19 The value is calculated from the characteristic peak intensity ratio of the terminal structure to 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 dimethyl sulfoxide was used as a standard substance. 1 The values ​​shown are calculated from the ratio of the characteristic peak intensities of the terminal structure based on H-NMR analysis and a standard substance. The molar amount of the compound is calculated by dividing the measured mass by the molecular weight calculated from the molecular formula, or by multiplying by the terminal group concentration. The solution kinematic viscosity of a 15% by mass solvent (Novec 7300) of a polymer of the monomer (hereinafter referred to as solution kinematic viscosity) is the value measured using a Canon-Fenske viscometer according to the method described in JIS Z8803:2011, and the film thickness is the value calculated from the following formula. The room temperature is 25°C. [Film thickness (μm)] = [Increase in substrate mass (g) before and after coating)] ÷ [Density of water / oil repellent agent (g / cm 3 )]÷[Substrate area (cm 2 ) ÷ 2 × 10,000

[0042] Synthesis Example 1 Synthesis of Compound (a-2) In a 2 L four-neck flask equipped with a thermometer, a nitrogen gas inlet, a reflux condenser, a stirrer, and a stirrer, a compound represented by the following formula (a-1) was added: (number average molecular weight of fluoropolyether group: about 1,450, terminal group (F in C(═O)F group) concentration: 6.69 × 10 -4 300.0 g (0.201 mol) of sodium bis(2-methoxyethoxy)aluminum hydride (70% by mass toluene solution), 240.5 g (0.833 mol) of sodium bis(2-methoxyethoxy)aluminum hydride, and 75.0 g of tetrahydrofuran (super-dehydrated, stabilizer-free) as a solvent were charged and aged at 55° C. for 20 hours. Thereafter, the reaction was stopped and the solvent was distilled off under reduced pressure to obtain 242.2 g of a product.

[0043] The resulting product is 1 H-NMR and 19It was confirmed by F-NMR that the compound was the compound represented by the following formula (a-2).

[0044] Synthesis Example 2 Synthesis of Compound (A) In a 200 mL four-neck flask equipped with a thermometer, a dry air inlet, a reflux condenser, a stirrer, and a stirrer, a compound represented by the following formula (a-2) was added. A compound represented by the formula (number average molecular weight of fluoropolyether group: about 1,450, terminal group (OH group) concentration: 6.76 × 10 -4 mol / g) 100.0g (6.76×10 -2 mol), 16.7 g (0.118 mol) of 2-isocyanatoethyl acrylate, and 0.02 g of 4-methoxyphenol were mixed, and then 0.24 g (4.25 × 10) of tetrakis(2-ethylhexyl) orthotitanate was added. -4 mol) was added, and the mixture was aged for 20 hours at 45° C. Thereafter, water was added to precipitate unreacted materials, which were then removed by filtration to obtain 94.0 g of a product.

[0045] The resulting product is 1 H-NMR and 19 F-NMR confirmed that the compound was the compound represented by the following formula (A):

[0046] Synthesis Example 3 Synthesis of Compound (B) 101.2 g of product was obtained in the same manner as in Synthesis Example 2, except that 16.7 g (0.118 mol) of 2-isocyanatoethyl acrylate was changed to 18.3 g (0.118 mol) of 2-isocyanatoethyl methacrylate.

[0047] The resulting product is 1 H-NMR and 19 F-NMR confirmed that the compound was the compound represented by the following formula (B):

[0048] Synthesis Example 4 Synthesis of Compound (c-2) In Synthesis Example 1, 300.0 g (0.201 mol) of the compound represented by the above formula (a-1) was added to a compound represented by the following formula (c-1): (number average molecular weight of fluoropolyether group: about 4,100, terminal group (F in C(═O)F group) concentration: 2.41 × 10-4 mol / g) 300.0g (7.23×10 -2 221.0 g of product was obtained in the same manner except that the temperature was changed to (mol).

[0049] The resulting product is 1 H-NMR and 19 It was confirmed by F-NMR that the compound was represented by the following formula (c-2).

[0050] Synthesis Example 5 Synthesis of Compound (C) In Synthesis Example 2, 100.0 g (6.76 × 10 -2 mol) to 100.0 g (2.42 × 10 -2 mol), and the amount of 2-isocyanatoethyl acrylate used was changed to 5.98 g (4.24 × 10 -2 In the same manner as above, except that the solvent was changed to (mol), 84.3 g of product was obtained.

[0051] The resulting product is 1 H-NMR and 19 F-NMR confirmed that the compound was the compound represented by the following formula (C):

[0052] Synthesis Example 6 Synthesis of Compound (d-2) In Synthesis Example 1, 300.0 g (0.201 mol) of the compound represented by the above formula (a-1) was added to a compound represented by the following formula (d-1): (fluoropolyether group number average molecular weight: about 1,500, terminal group (OH group) concentration: 6.47 × 10 -4 In the same manner as above, except that the amount of the toluene was changed to 300.0 g (0.194 mol / g), 254.4 g of product was obtained.

[0053] The resulting product is 1 H-NMR and 19 It was confirmed by F-NMR that the compound was represented by the following formula (d-2).

[0054] Synthesis Example 7 Synthesis of Compound (D) In ​​Synthesis Example 2, 100.0 g (6.76 × 10 -2mol) to 100.0 g (6.55 × 10 -2 The same procedure was repeated except that the amount of 2-isocyanatoethyl acrylate used was changed to 16.2 g (0.115 mol) and the amount of 2-isocyanatoethyl acrylate used was changed to 16.2 g (0.115 mol), to obtain 80.2 g of product.

[0055] The resulting product is 1 H-NMR and 19 It was confirmed by F-NMR that the compound was the compound represented by the following formula (D).

[0056] Synthesis Example 8 Synthesis of Compound (E) (Comparative Product) In Synthesis Example 2, 100.0 g (6.76 × 10 -2 mol) is reacted with the compound represented by the following formula (e-1): A compound represented by the formula (number average molecular weight of fluoropolyether group: about 450, terminal group (OH group) concentration: 2.07 × 10 -3 In a similar manner, except that the amount of 2-isocyanatoethyl acrylate used was changed to 51.2 g (0.363 mol), 105.6 g of product was obtained.

[0057] The resulting product is 1 H-NMR and 19 F-NMR confirmed that the compound was the compound represented by the following formula (E):

[0058] Synthesis Example 9: Synthesis of Compound (F) (Comparative Product) In Synthesis Example 2, 100.0 g (6.76 × 10 -2 mol) is represented by the following formula (f-1): A compound represented by the formula (number average molecular weight of fluoropolyether group: about 5,760, terminal group (OH group) concentration: 1.73 × 10 -4 mol / g) 100.0g (1.73×10 -2 mol), and the amount of 2-isocyanatoethyl acrylate used was changed to 4.26 g (3.02 × 10 -2 74.1 g of product was obtained in the same manner except that the temperature was changed to (mol).

[0059] The resulting product is 1H-NMR and 19 F-NMR confirmed that the compound was the compound represented by the following formula (F):

[0060] Synthesis Example 10: Synthesis of Compound (G) (Comparative Product) In Synthesis Example 2, 100.0 g (6.76 × 10 -2 In the same manner as above, except that the amount of 2-isocyanatoethyl acrylate used was changed to 70.5 g (0.500 mol), 126.1 g of product was obtained.

[0061] The resulting product is 1 H-NMR and 19 F-NMR confirmed that the compound was the compound represented by the following formula (G):

[0062] Example 1 In a 200 mL four-neck flask equipped with a thermometer, a nitrogen gas inlet, a reflux condenser, a stirrer, and a stirrer, the compound of the following formula (A) obtained in Synthesis Example 2 above was added. (Rf in general formula (I) corresponds to a number average molecular weight of about 1,450, and the terminal group (acryloyloxy group) concentration is 6.18 × 10 -4 mol / g) 40.0g (2.47×10 -2 mol), 60.0 g of Novec 7300 (manufactured by 3M) as a solvent, and 0.200 g (1.04 × 10) of V-59 (2,2′-azobis(2-methylbutyronitrile)) as a radical polymerization initiator. -3 The resulting mixture was reacted at 65°C for 24 hours while passing nitrogen gas through it. The solution kinematic viscosity of the resulting polymer of the monomers was 52.0 mm 2 Thereafter, Novec 7300 was added so that the active ingredient concentration was 15% by mass, thereby preparing a coating liquid of a polymer of the monomer represented by formula (A).

[0063] [Example 2] A monomer was prepared by converting a monomer represented by formula (A) into a monomer represented by the following formula (B) obtained in Synthesis Example 3 (Rf in general formula (I): number average molecular weight: approximately 1,450; terminal group (methacryloyloxy group) concentration: 6.12 × 10 -4 mol / g) 40.0g (2.45×10 -2 The same procedure as in Example 1 was repeated except that the polymer was changed to a polymer of the monomer (dissolution kinematic viscosity: 40.5 mm 2 / s) and a coating solution were prepared.

[0064] [Example 3] A monomer was prepared by converting a monomer represented by formula (A) into a monomer represented by the following formula (C) obtained in Synthesis Example 5 (Rf in general formula (I): number average molecular weight: approximately 4,100, terminal group (acryloyloxy group) concentration: 2.34 × 10 -4 mol / g) 40.0g (9.36×10 -3 The same procedure as in Example 1 was repeated except that the polymer was changed to a polymer of the monomer (the solution kinematic viscosity was 53.5 mm mol). 2 / s) and a coating solution were prepared.

[0065] [Example 4] A monomer was prepared by converting a monomer represented by formula (A) into a monomer represented by formula (D) obtained in Synthesis Example 7 (Rf in general formula (I): number average molecular weight: approximately 1,500, terminal group (acryloyloxy group) concentration: 5.98 × 10 -4 mol / g) 40.0g (2.39×10 -2 The same procedure as in Example 1 was repeated except that the polymer was changed to a polymer of the monomer (dissolution kinematic viscosity: 45.5 mm 2 / s) and a coating solution were prepared.

[0066] [Comparative Example 1] A monomer was prepared by converting a monomer represented by formula (A) into a monomer represented by the following formula (E) obtained in Synthesis Example 8 (Rf in general formula (I) corresponds to a number average molecular weight of about 450, and has a terminal group (acryloyloxy group) concentration of 1.60 × 10). -3 mol / g) 40.0g (6.40×10 -2The same procedure as in Example 1 was repeated except that the polymer was changed to a polymer of the monomer (the solution kinematic viscosity was 78.2 mm mol). 2 / s) and a coating solution were prepared.

[0067] [Comparative Example 2] A monomer was prepared by converting a monomer represented by formula (A) into a monomer represented by formula (F) obtained in Synthesis Example 9 (Rf in general formula (I): number average molecular weight: approximately 5,760; terminal group (acryloyloxy group) concentration: 1.68 × 10 -4 mol / g) 40.0g (6.72×10 -3 The same procedure as in Example 1 was repeated except that the polymer was changed to a polymer of the monomer (dissolution kinematic viscosity: 40.5 mm 2 / s) and a coating solution were prepared.

[0068] Comparative Example 3 Monomers were prepared by converting the monomer represented by formula (A) into the monomer represented by formula (G) obtained in Synthesis Example 10 above (a urethane-modified acrylate derived from a perfluorohexanoic acid (PFHxA)-related substance that is of concern for its potential for accumulation in the human body) (terminal group (acryloyloxy group) concentration: 2.04×10 -3 mol / g) 40.0g (8.14×10 -2 The same procedure as in Example 1 was repeated except that the polymer was changed to a polymer of the monomer (the solution kinematic viscosity was 32.8 mm mol). 2 / s) and a coating solution were prepared.

[0069] [Preparation of Glass Samples] The coating solutions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were dip-coated onto glass slides (S1127, 76 mm x 26 mm, manufactured by Matsunami Glass Industrial Co., Ltd.) under the following conditions to prepare glass samples with coating thicknesses of 1.0 to 1.2 μm. <Dip coating conditions> Coating device: Tabletop dip coater (DT-0303-S3, manufactured by SDI Corporation) Immersion time: 30 seconds Pull-up speed: 0.3 mm / sec Drying after coating: Room temperature, 30 minutes

[0070] [Preparation of PTFE Samples] A fluorine-based solvent (Novec7300 / m-hexafluoroxylene = 7:3 (parts by mass)) was added to the coating solutions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 so that the active ingredient concentration was 3% by mass, to prepare diluted solutions. Subsequently, a PTFE (polytetrafluoroethylene) porous membrane (PF-100, manufactured by ADVANTEC) cut to 70 mm x 26 mm was dip-coated under the following conditions to prepare a PTFE sample to which 0.0692 g of the active ingredient of the diluted solution was attached. <Dip Coating Conditions> Coating device: Tabletop dip coater (DT-0303-S3, manufactured by SDI Corporation) Immersion time: 30 seconds Pull-up speed: 3.0 mm / sec Drying after coating: Room temperature, 30 minutes

[0071] [Water Contact Angle, Hexadecane (HD) Contact Angle] For the glass samples prepared above, the contact angles (water repellency and oil repellency) of the coating to water and hexadecane (HD) were measured using a contact angle meter Drop Master (DMo-701SA, manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μL, temperature: 25° C., relative humidity: 40%). The measurement was performed by photographing pure water 3 seconds after dropping or hexadecane 1 second after dropping with a CCD camera connected to the contact angle meter, and then analyzing the droplet image using FAMAS, the contact angle analysis software attached to the 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 were as follows. The results (initial water contact angle or initial HD contact angle) are shown in Table 2. Initially, both the Examples and Comparative Examples showed good water repellency. [Analysis conditions] Method: Sessile drop 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 ○: 125° or more △: 115° or more, less than 125° ×: Less than 115° HD contact angle ○: 75° or more △: 65° or more, less than 75° ×: Less than 65°

[0072] [Initial Oil Repellency] The initial oil repellency was evaluated in accordance with AATCC Test Method 118-2020. A drop of the test liquid shown in Table 1 was dropped onto the PTFE sample obtained above using a Pasteur pipette. If the drop did not penetrate after 30 seconds, the test liquid was deemed to have passed. The highest grade of the test liquid that passed was designated as the oil repellency. The results are shown in Table 2.

[0073]

[0074] [Heat Resistance] The PTFE samples evaluated for initial oil repellency as described above were left at 150°C for 100 hours. Thereafter, the oil repellency after the heat resistance test was measured in accordance with AATCC Test Method 118-2020, and the heat resistance was evaluated based on the following criteria. The results are shown in Table 2. [Evaluation Criteria] ○: [Initial oil repellency] - [Oil repellency after heat resistance test] = Grade 0 △: [Initial oil repellency] - [Oil repellency after heat resistance test] = Grade 1 ×: [Initial oil repellency] - [Oil repellency after heat resistance test] ≧ Grade 2

[0075] [Presence or Absence of PFOA, PFHxA, and Related Substances] The monomers in the coating solutions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated as follows: those that did not contain PFOA (perfluorooctanoic acid), which has been pointed out as having a potential for accumulation in the human body and the environment, and PFHxA (perfluorohexanoic acid), which is feared to pose a similar risk, and their related substances were evaluated as ○; those that contained PFOA, PFHxA, and their related substances were evaluated as ×. The results are shown in Table 2.

[0076]

Claims

1. A compound represented by the following general formula (I): (wherein R is a hydrogen atom, a halogen atom, an alkyl group or an aryl group; X is a single bond or an unsubstituted or substituted divalent hydrocarbon group which may contain one or more bonds selected from an oxygen atom, an amino bond, an amide bond, a urethane bond and a urea bond; and Rf is a monovalent fluoropolyether group which is end-capped with a perfluoroalkyl group having 5 or less carbon atoms and has a number average molecular weight of 1,000 to 5,000.) 2. The water / oil repellent according to claim 1, wherein R in the general formula (I) is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, or a phenyl group.

3. The water / oil repellent according to claim 1, wherein X in general formula (I) is any one selected from a single bond, an unsubstituted or substituted alkylene group having 1 to 15 carbon atoms which may contain an oxygen atom, and a structure represented by the following general formula (1) or (2): (In each of formulas (1) and (2), the position indicated by * is the bonding position to the carbon atom in general formula (I), and the position indicated by ** is the bonding position to the Rf group in general formula (I).) 4. The water and oil repellent according to claim 1, wherein the Rf group in the general formula (I) is represented by the following general formula (3) or (4): (In the formula, n is an integer from 5 to 28.) (In the formulae, p is an integer of 0 to 41, and q is an integer of 0 to 73, and the numbers satisfy p+q=8 to 73. The repeating units shown in parentheses with p and q may be bonded randomly. In each formula, the position indicated by ** is the bonding position to X in general formula (I).) 5. The water- and oil-repellent agent according to claim 1, which when applied to a glass plate, gives a coating having a water contact angle of 115° or more.

6. The water- and oil-repellent agent according to claim 1, which when applied to a glass plate, gives a coating having a hexadecane contact angle of 75° or more.

7. The water and oil repellent agent according to claim 1, which when applied to a substrate, gives a coating having an oil repellency of grade 7 or higher according to AATCC test method 118-2020, and which does not decrease in oil repellency from the initial level after heating at 150°C for 100 hours.

8. The water and oil repellent according to claim 7, wherein the substrate to which the agent is applied is a fiber or a porous film.

9. The water- and oil-repellent agent according to claim 8, wherein the porous film is made of PTFE (polytetrafluoroethylene).

10. An article having a coating of the water and oil repellent agent according to any one of claims 1 to 9 on its surface.

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