Water-repellent oil-repellent agent and article

Abstract

A water-and oil-repellent agent, which contains a polymer of a monomer represented by general formula (I), exhibits good water and oil repellency not only in the initial stage but also under heat-resistant conditions, although the number of carbon atoms in a perfluoroalkyl group is less than 6 (5 or less). # imgabs0 # (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 optionally containing one or more elements selected from the group consisting of an oxygen atom, an amino bond, an amide bond, a urethane bond, and a urea bond, and Rf is a monovalent fluoropolyether group having a molecular weight of 1000-5000 and having a terminal terminated by a perfluoroalkyl group having 5 or less carbon atoms. ).

Description

Technical Field

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

[0002] Conventionally, polymers of fluorinated acrylic or methacrylic monomers as described in Patent Document 1 (Japanese Patent Publication No. 1-42983) and Patent Document 2 (Japanese Patent Application Laid-Open No. 7-109317) have been applied to substrates to enhance their surface modification functions such as water and oil repellency.

[0003] To achieve high water and oil repellency and other surface modification functions, long-chain perfluoroalkyl groups with carbon atoms of 8 or more are used. However, long-chain perfluorocarboxylic acids with perfluoroalkyl groups with carbon atoms of 8 or more, such as perfluorooctanoic acid (PFOA), have been shown to accumulate in the human body.

[0004] To reduce risks to organisms and the environment, PFOA is replaced with, for example, perfluorohexanoic acid (PFHxA) having a carbon number of 6. For example, Patent Document 3 (Japanese Patent Application Laid-Open No. 2020-050757) discloses a surface modifier containing a polymer of a (meth)acrylic acid derivative containing a perfluoroalkyl group having a carbon number of 6 as an active ingredient.

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

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Publication No. 1-42983

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 7-109317

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 2020-050757 Summary of the Invention

[0011] Problems to be solved by the invention

[0012] The present invention is completed in view of the above-mentioned actual situation, and its purpose is to provide a water- and oil-repellent agent that shows good water- and oil-repellency not only in the initial stage but also under heat-resistant conditions, although the number of carbon atoms of the perfluoroalkyl group is less than 6 (5 or less), and an article having a coating film of the water- and oil-repellent agent on the surface.

[0013] Means for solving problems

[0014] The present inventors have conducted intensive research to achieve the above-mentioned objectives and have discovered that a water- and oil-repellent agent comprising a polymer obtained by polymerizing a monovalent fluoropolyether group having a molecular weight of 1000 to 5000 and an acrylate-based monomer having a specific linking group structure, which is terminated by a perfluoroalkyl group having 5 or less carbon atoms, maintains good water- and oil-repellency not only in the initial stage but also under heat-resistant conditions, thereby completing the present invention.

[0015] Therefore, the present invention provides the following water- and oil-repellent agents and articles.

[0016] [1] A water- and oil-repellent agent comprising a polymer of a monomer represented by the following general formula (I).

[0017] [Chemistry 1]

[0018]

[0019] (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 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 Rf is a monovalent fluoropolyether group having a molecular weight of 1000 to 5000 and end-capped with a perfluoroalkyl group having 5 or less carbon atoms.)

[0020] [2] The water- and oil-repellent agent according to [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.

[0021] [3] The water- and oil-repellent according to [1] or [2], wherein X in the general formula (I) is any one 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 formulae (1) to (5).

[0022] [Chemistry 2]

[0023]

[0024] [Chemistry 3]

[0025]

[0026] [Chemistry 4]

[0027]

[0028] [Chemistry 5]

[0029]

[0030] [Chemistry 6]

[0031]

[0032] (In each of formulae (1) to (5), the site indicated by * is a bonding site to the oxygen atom in the general formula (I), and the site indicated by ** is a bonding site to the Rf group in the general formula (I).)

[0033] [4] The water- and oil-repellent agent according to any one of [1] to [3], wherein the Rf group in the general formula (I) is represented by the following general formula (7) or (8).

[0034] [Chemistry 7]

[0035]

[0036] (Wherein, n is an integer from 5 to 28.)

[0037] [Chemistry 8]

[0038] CF3-(OCF2CF2) p -(OCF2) q -OCF2- (8)

[0039] (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. The repeating units shown in parentheses with p and q may be randomly bonded.)

[0040] [5] The water- and oil-repellent according to any one of [1] to [4], which can form a film having a water contact angle of 115° or greater when applied to a glass plate.

[0041] [6] The water- and oil-repellent according to any one of [1] to [5], which can form a film having a hexadecane contact angle of 75° or greater when applied to a glass plate.

[0042] [7] The water- and oil-repellent according to any one of [1] to [6], which can form a film having an oil repellency of grade 7 or higher according to AATCC test method 118-2020 when applied to a substrate and an oil repellency of not less than the initial oil repellency after heating at 150°C for 100 hours.

[0043] [8] The water- and oil-repellent agent according to any one of [1] to [7], wherein the substrate to be coated is a fiber or a porous film.

[0044] [9] The water- and oil-repellent according to [8], wherein the porous membrane comprises PTFE (polytetrafluoroethylene).

[0045]

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

[0046] Effects of the Invention

[0047] According to the water- and oil-repellent of the present invention, there can be provided a water- and oil-repellent which exhibits good water- and oil-repellency not only initially but also under heat-resistant conditions, although the number of carbon atoms in the perfluoroalkyl portion is less than 6 (5 or less), and an article having a coating film of the water- and oil-repellent on the surface. DETAILED DESCRIPTION

[0048] The water- and oil-repellent agent of the present invention contains a polymer of a monomer (monomer) represented by the following general formula (I).

[0049] [Chemistry 9]

[0050]

[0051] (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 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 Rf is a monovalent fluoropolyether group having a molecular weight of 1000 to 5000 and end-capped with a perfluoroalkyl group having 5 or less carbon atoms.)

[0052] In the general formula (I), R is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group. 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.

[0053] In the general formula (I), X is a single bond, or an unsubstituted or substituted divalent hydrocarbon group that 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 (connecting group) connecting the Rf group and the oxygen atom at the terminal of the acrylate. Examples of the 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 include divalent hydrocarbon groups having 1 to 20 carbon atoms, such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), alkylene groups such as hexamethylene and octamethylene, arylene groups such as phenylene, or combinations of two or more of these groups (alkylene-arylene groups, etc.). The divalent hydrocarbon group having 1 to 20 carbon atoms may contain one or more 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—). Furthermore, the divalent hydrocarbon group may be a substituted divalent hydrocarbon group in which some or all of the hydrogen atoms bonded to carbon atoms are substituted with halogen atoms such as fluorine or iodine. Furthermore, the divalent hydrocarbon group having 1 to 20 carbon atoms may include two amide bonds repeated.

[0054] X is preferably a single bond, an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, or a structure represented by the following general formulae (1) to (5).

[0055] [Chemistry 10]

[0056]

[0057] [Chemistry 11]

[0058]

[0059] [Chemistry 12]

[0060]

[0061] [Chemistry 13]

[0062]

[0063] [Chemistry 14]

[0064]

[0065] (In each of formulae (1) to (5), the site indicated by * is a bonding site to the oxygen atom in the general formula (I), and the site indicated by ** is a bonding site to the Rf group in the general formula (I).)

[0066] In the general formula (I), Rf is a monovalent fluoropolyether group having a molecular weight of 1000 to 5000, the terminal of which is capped with a perfluoroalkyl group having 5 or less carbon atoms, preferably a monovalent perfluoropolyether group having a molecular weight of 1000 to 5000, and more preferably contains a repeating unit represented by the following general formula (6).

[0067] [Chemistry 15]

[0068]

[0069] (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 is a number that satisfies a+b+c=5 to 73. The repeating units shown in parentheses with a, b, and c may be randomly combined.)

[0070] Examples of the repeating unit represented by the general formula (6) include units represented by the following formulas.

[0071] [Chemistry 16]

[0072]

[0073] Among these, the repeating unit represented by the following formula is particularly preferred.

[0074] [Chemistry 17]

[0075]

[0076] The end of Rf (monovalent fluoropolyether group) is replaced by a perfluoroalkyl group with a carbon number of 5 or less, such as CF3-, C2F5-(CF3CF2-), C3F7-(CF3CF2CF2-, (CF3)2CF-), C4F9-(CF3(CF2)3-), C5F 11 -(CF3(CF2)4-) and other end-capping.

[0077] In the present invention, preferred Rf groups are structures represented by the following general formulas (7) and (8).

[0078] [Chemistry 18]

[0079]

[0080] (Wherein, n is an integer from 5 to 28.)

[0081] [Chemistry 19]

[0082] CF3-(OCF2CF2) p -(OCF2) q -OCF2- (8)

[0083] (In the formula, p is an integer of 0 to 41, q is an integer of 0 to 73, and is a number satisfying p+q=8 to 73. The repeating units shown in parentheses with p and q may be randomly bonded.)

[0084] The Rf group is more preferably a structure represented by the following general formula (9).

[0085] [Chemistry 20]

[0086]

[0087] In the present invention, the molecular weight of the Rf group is 1000 to 5000, preferably 1300 to 3500. If the molecular weight of Rf is less than 1000, the heat resistance (water and oil repellency after the heat resistance test) of the film is poor. If it exceeds 5000, not only is it difficult to handle during polymerization due to high viscosity, but the initial water and oil repellency and heat resistance (water and oil repellency after the heat resistance test) of the film are poor. In the present invention, the molecular weight of the Rf group can be, for example, 19 Confirmed by F-NMR, etc.

[0088] Examples of the monomer represented by the general formula (I) include monomers represented by the following formulae.

[0089] [Chemistry 21]

[0090]

[0091] [Chemistry 22]

[0092]

[0093] [Chemistry 23]

[0094]

[0095] [Chemistry 24]

[0096]

[0097] (In the formula, n, p, and q are the same as above.)

[0098] The polymer according to the present invention can be obtained by dissolving the monomer represented by the formula (I) in a solvent and polymerizing it using a radical polymerization initiator by a known method such as solution polymerization.

[0099] The solvent used in the method for manufacturing the polymer of the present invention is not particularly limited as long as it can dissolve the monomer represented by the formula (I), and is preferably a fluorine-based solvent. As a fluorine-based solvent, for example, Novec7300, Novec7200, Novec7100 (3M Company), AC-6000, AE-3000 (AGC Co., Ltd.), hexafluoroacetone, hexafluoroisopropanol, hexafluoro-m-xylene (Central Glass Co., Ltd.) and the like can be listed. Among them, from the viewpoint of solubility, Novec7300 is preferred.

[0100] The amount of the solvent used is not particularly limited, but is preferably 50 to 2000 parts by mass, particularly preferably 100 to 1000 parts by mass, and further preferably 200 to 400 parts by mass, relative to 100 parts by mass of the monomer represented by formula (I).

[0101] Examples of the radical polymerization initiator that can be used in the method for producing the polymer according to the present invention include dimethyl azobisisobutyrate (V-601), cumene hydroperoxide, succinic acid peroxide, di-tert-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-methylamide oxime) dihydrochloride, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutylamidine) dihydrochloride, 2,2'-azobis[2-(2-

[0014] The present invention also includes azo compounds such as tert-butylperoxyimidazolin-2-yl)propane] and its disulfate, 2,2'-azobisisobutyronitrile (AIBN), 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethylhexane-2,5-dihydroperoxide, tert-butyl-α-cumyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxyisopropylcarbonate, tert-butyl hydroperoxide, α,α'-di(tert-butylperoxy)-p-diisopropylbenzene, organic peroxides, potassium persulfate, sodium persulfate, ammonium persulfate, and the like. These free radical polymerization initiators may be used alone or in combination of two or more.

[0102] The amount of the radical polymerization initiator used is not particularly limited, but is preferably 0.05 to 10 parts by mass, particularly preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the monomer represented by formula (I).

[0103] The polymerization conditions for the monomer represented by the formula (I) in the polymerization method using the above solvent and radical polymerization initiator are preferably set to be in an inert gas atmosphere at 40 to 120° C., especially 65 to 70° C., for 4 to 30 hours, especially 18 to 24 hours.

[0104] The 15% by mass solvent kinetic viscosity of the polymer of the monomer represented by the formula (I) thus obtained is preferably 1 to 100 mm 2 / s, more preferably 5 to 50 mm 2 / s. If the dissolution kinematic viscosity is too small, the surface properties when applied to the substrate are sometimes low, and if it is too large, the workability during application is sometimes deteriorated. Furthermore, the dissolution kinematic viscosity can be measured using a Canon-Fenske viscometer using the method described in JIS Z8803:2011. In addition, as a solvent, there is no particular limitation as long as it can dissolve the polymer of the monomer represented by the formula (I). From the aspects of solubility and stability, fluorine-based solvents are preferred. As fluorine-based solvents, for example, Novec7300, Novec7200, Novec7100 (manufactured by 3M Company), AC-6000, AE-3000 (manufactured by AGC Corporation), hexafluoroacetone, hexafluoroisopropanol, hexafluoro-m-xylene (manufactured by Central Glass Co., Ltd.) and the like can be cited. Among them, from the viewpoint of solubility, Novec7300 is preferred.

[0105] The water- and oil-repellent agent of the present invention contains the polymer of the monomer represented by the above-mentioned formula (I). The water- and oil-repellent agent of the present invention is generally provided as a solvent solution of the above-mentioned polymer. Wherein, as the polymer amount (concentration of polymer) in the solvent solution, it is preferably 1 to 50 mass %, particularly preferably 3 to 30 mass %, and especially preferably 3 to 15 mass %.

[0106] As long as the solvent for water and oil repellent can dissolve the monomer, it is not particularly limited, preferably fluorine-based solvent.As fluorine-based solvent, for example, Novec7300, Novec7200, Novec7100 (3M company system), AC-6000, AE-3000 (AGC Co., Ltd. system), hexafluoroacetone, hexafluoroisopropanol, hexafluoro-m-xylene (Central Glass Co., Ltd. system) etc. can be listed.Wherein, from the viewpoint of solubility, preferably Novec7300.Again, as the solvent for water and oil repellent, the solvent used in the manufacture method of above-mentioned polymer can be directly used, in order to regulate the concentration of polymer, above-mentioned solvent can be further added after the manufacture of polymer.

[0107] As a method for applying the water- and oil-repellent agent of the present invention to a substrate, for example, spin coating, dip coating, spray coating, roll coating, meniscus coating, or screen printing can be used.

[0108] Water- and oil-repellent agent of the present invention is by making solvent drying after coating to base materials such as glass, fiber, porous-film, thereby easily forms tunic on substrate surface.Specifically, preferably dry 30 minutes~24 hours at room temperature (25 ℃ ± 10 ℃).In addition, in order to accelerate drying, can be in the scope that does not affect base material, for example, heat about 30 seconds~24 hours at 40~150 ℃.This tunic is owing to containing fluorine atom in polymer, therefore shows excellent water- and oil-repellent property.Therefore, can be used as the water- and oil-repellent coating agent of glass, fiber, porous-film etc., particularly fiber, porous-film.

[0109] As the fibrous base material of coating water- and oil-repellent agent of the present invention, for example, can enumerate forms such as fiber, yarn, cloth.As the fiber constituting this fibrous base material, can enumerate glass fibre, 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, aramid fiber, poly-p-phenylene benzobisoxazole fiber, vegetable fiber, cellulose fiber and lignin fiber etc..This fiber can be used alone a kind of, also can be by two or more and use.

[0110] As the porous membrane substrate of coating water- and oil-repellent agent of the present invention, for example, nonwoven fabrics, perforated membrane, microporous membrane, porous body etc. can be enumerated.As the material constituting the porous membrane substrate, resins such as PTFE (polytetrafluoroethylene), ceramics, metal etc. can be enumerated, preferably PTFE (polytetrafluoroethylene).

[0111] The film thickness of the coating is appropriately selected depending on the type of substrate, and is generally 0.01 to 50 μm, particularly 1 to 10 μm. The film thickness can be calculated, for example, using the following formula.

[0112] [Film thickness (μm)] = [Increase in substrate mass before and after coating (g)] ÷ [Density of water- and oil-repellent agent (g / cm 3 )]÷[Substrate area (cm 2 )]×10000

[0113] Alternatively, the film thickness can be measured by spectroscopic reflectivity measurement, X-ray reflectivity measurement, spectroscopic ellipsometry, fluorescent X-ray measurement, or the like.

[0114] Examples of articles having a coating film of the water- and oil-repellent agent of the present invention on their surfaces include automotive products, fiber products, nonwoven fabrics, and filters used in the presence of an organic solvent liquid or its vapor.

[0115] The contact angle for water (water contact angle) of the film formed by applying the water- and oil-repellent agent of the present invention to a glass plate at a temperature of 25°C and a relative humidity of 40% is 115° or more, preferably 120° or more. It should be noted that in the present invention, the contact angle for water is a 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.

[0116] In addition, the contact angle for hexadecane (hexadecane (HD) contact angle) at a temperature of 25°C and a relative humidity of 40% for a film formed by applying the water- and oil-repellent agent of the present invention to a glass plate is preferably 75° or more, preferably 78° or more. It should be noted that in the present invention, the contact angle for hexadecane is a value measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) at a droplet of 2 μl.

[0117] Furthermore, it is preferred 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 AATCC test method 118-2020, and the oil repellency after heating at 150° C. for 100 hours does not decrease from the initial oil repellency.

[0118] Example

[0119] The present invention is specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, the molecular weight of the fluoropolyether group (Rf in the general formula (I)) is represented by the formula based on 19 The values ​​are calculated from the ratio of the characteristic peak intensities of the terminal structure and the main chain structure as determined by F-NMR analysis. The kinematic viscosity of the monomeric polymer dissolved in a 15% solvent (Novec 7300) (hereinafter referred to as the dissolved kinematic viscosity) is measured using a Canon-Fenske viscometer according to the method described in JIS Z8803:2011. The film thickness is calculated using the following formula. Room temperature refers to 25°C.

[0120] [Film thickness (μm)] = [Increase in substrate mass before and after coating (g)] ÷ [Density of water- and oil-repellent agent (g / cm 3 )]÷[Substrate area (cm 2 )]×10000

[0121] [Example 1]

[0122] A 200 ml four-necked flask equipped with a thermometer, an inert gas inlet, a reflux condenser, and a stirrer was charged with the following formula (A):

[0123] [Chemistry 25]

[0124]

[0125] 30 parts by mass of the monomer represented by (molecular weight of Rf in general formula (I); equivalent to about 1430), 70 parts by mass of Novec 7300 (manufactured by 3M Co.) as a solvent, and 0.15 parts by mass of PERBUTYL O (tert-butyl peroxy-2-ethylhexanoate, manufactured by NOF Corporation) as a radical polymerization initiator were reacted at 70°C for 24 hours while flowing nitrogen. The melt kinematic viscosity of the resulting polymer of the monomer was 6.17 mm 2 Then, Novec 7300 was added so that the active ingredient concentration became 15% by mass to prepare a coating liquid of a polymer of the monomer represented by formula (A).

[0126] [Example 2]

[0127] A polymer (melting kinematic viscosity: 5.90 mm) of the monomer was prepared in the same manner as in Example 1 except that the monomer represented by the following formula (B) was used instead of the monomer represented by the formula (A) (molecular weight of Rf in the general formula (I): equivalent to about 1430). 2 / s) and coating liquid.

[0128] [Chemistry 26]

[0129]

[0130] [Example 3]

[0131] A polymer (melting kinematic viscosity: 6.30 mm) of the monomer was prepared in the same manner as in Example 1 except that the monomer of formula (A) was changed to the monomer represented by the following formula (C) (molecular weight of Rf in general formula (I): equivalent to about 1430). 2 / s) and coating liquid.

[0132] [Chemistry 27]

[0133]

[0134] [Example 4]

[0135] A polymer (melting kinematic viscosity: 7.36 mm) of the monomer was prepared in the same manner as in Example 1 except that the monomer represented by the following formula (D) was changed from the monomer represented by the formula (A) (molecular weight of Rf in the general formula (I): equivalent to about 4100). 2 / s) and coating liquid.

[0136] [Chemistry 28]

[0137]

[0138] [Example 5]

[0139] A polymer (melting kinematic viscosity: 6.23 mm) of the monomer was prepared in the same manner as in Example 1 except that the monomer represented by the following formula (E) was changed from the monomer represented by the formula (A) (molecular weight of Rf in the general formula (I): equivalent to about 1500). 2 / s) and coating liquid.

[0140] [Chemistry 29]

[0141]

[0142] [Comparative Example 1]

[0143] A polymer (melting kinematic viscosity: 73.6 mm) of the monomer was prepared in the same manner as in Example 1 except that the monomer of formula (A) was changed to a monomer represented by the following formula (F) (molecular weight of Rf in general formula (I): equivalent to about 432). 2 / s) and coating liquid.

[0144] [Chemistry 30]

[0145]

[0146] [Comparative Example 2]

[0147] A polymer (melting kinematic viscosity: 9.58 mm) of the monomer was prepared in the same manner as in Example 1 except that the monomer of formula (A) was changed to a monomer represented by the following formula (G) (molecular weight of Rf in general formula (I): equivalent to about 5740). 2 / s) and coating liquid.

[0148] [Chemistry 31]

[0149]

[0150] [Comparative Example 3]

[0151] A polymer (melting kinematic viscosity: 12.0 mm) of the monomer was prepared in the same manner as in Example 1 except that the monomer of formula (A) was changed to the monomer of formula (H) below (urethane-modified acrylate derived from a perfluorohexanoic acid (PFHxA)-related substance that is concerned about accumulation in the human body). 2 / s) and coating liquid.

[0152] [Chemistry 32]

[0153]

[0154] [Production of glass samples]

[0155] The coating liquids prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were dip-coated on slide glass (S1127, 76 mm×26 mm, manufactured by Matsunami Glass Industries, Ltd.) under the following conditions to prepare glass samples having a coating thickness of 2.0 to 2.2 μm.

[0156] Dip coating conditions

[0157] Coating equipment: Desktop dip coater (manufactured by SDI Co., Ltd.)

[0158] Dipping time: 30 seconds

[0159] Lifting speed: 0.3mm / s

[0160] Drying after coating: Room temperature, 30 minutes

[0161] [Preparation of PTFE samples]

[0162] A fluorinated solvent (Novec 7300 / hexafluoro-m-xylene = 7:3 (parts by mass)) was added to the coating solutions prepared in Examples 1-5 and Comparative Examples 1-3 to obtain a 3% active ingredient concentration to prepare a diluted solution. Next, a PTFE (polytetrafluoroethylene) porous membrane (PF-100, manufactured by ADVANTEC) cut into 70 mm x 26 mm pieces was dip-coated under the following conditions to produce a PTFE sample to which 0.0692 g of the active ingredient from the diluted solution was attached.

[0163] Dip coating conditions

[0164] Coating equipment: Desktop dip coater (manufactured by SDI Co., Ltd.)

[0165] Dipping time: 30 seconds

[0166] Lifting speed: 3.0mm / s

[0167] Drying after coating: Room temperature, 30 minutes

[0168] [Water contact angle, hexadecane (HD) contact angle]

[0169] The contact angle of the glass sample obtained above with respect to water and the contact angle with respect to hexadecane (HD) were measured using a contact angle meter under the following conditions.

[0170] Contact Angle Measurement Conditions

[0171] Measuring device: Drop Master (manufactured by Kyowa Interface Science Co., Ltd.)

[0172] Droplet: 2μL

[0173] Temperature: 25℃

[0174] Relative humidity: 40%

[0175] [Evaluation criteria]

[0176] Pure water contact angle

[0177] ○: 125° or more

[0178] △: 115° or more and less than 125°

[0179] ×: less than 115°

[0180] HD contact angle

[0181] ○: 75° or above

[0182] Δ: 65° or more and less than 75°

[0183] ×: less than 65°

[0184] [Initial oil repellency]

[0185] Initial oil repellency was evaluated according to AATCC test method 118-2020. For the PTFE sample obtained above, a drop of the test solution shown in Table 1 was dripped using a transfer tool pipette. After 30 seconds, if the droplet did not penetrate, the test solution was considered qualified. The highest grade of the qualified test solution was set as the oil repellency. The results are shown in Table 2.

[0186] [Table 1]

[0187] Test fluid grade n-hexane 8 n-octane 7 n-Decane 6 n-Dodecane 5 n-Tetradecane 4 n-Hexadecane 3 Refined mineral oil / n-hexadecane = 65 / 35 (volume %) 2 refined mineral oil 1

[0188] [Heat resistance]

[0189] The PTFE samples evaluated for initial oil repellency were left at 150°C for 100 hours. The oil repellency after the heat test was measured according to AATCC Test Method 118-2020, and the heat resistance was evaluated based on the following criteria. The results are shown in Table 2.

[0190] [Evaluation criteria]

[0191] ○: [Initial oil repellency] - [Oil repellency after heat resistance test] = 0 level

[0192] Δ: [Initial oil repellency] - [Oil repellency after heat resistance test] = 1 level

[0193] ×: [Initial oil repellency] - [Oil repellency after heat resistance test] ≥ 2 levels

[0194] [Contains PFOA and PFHxA related substances]

[0195] Regarding the monomers in the coating solutions prepared in Examples 1 to 5 and Comparative Examples 1 to 3, samples containing no PFOA (perfluorooctanoic acid), which is known to accumulate in the human body and the environment, or PFHxA (perfluorohexanoic acid)-related substances, which pose a similar risk, were rated as positive, while samples containing PFOA and PFHxA-related substances were rated as negative. The results are shown in Table 2.

[0196] [Table 2]

[0197]

Claims

1. A water- and oil-repellent agent comprising a polymer of a monomer represented by the following general formula (I), [Chemistry 1] 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 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 Rf is a monovalent fluoropolyether group having a molecular weight of 1000 to 5000 and end-capped with a perfluoroalkyl group having 5 or less carbon atoms.

2. The water- and oil-repellent agent according to claim 1, wherein In the general formula (I), R 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 agent according to claim 1, wherein X in the general formula (I) is any one selected from a single bond, an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, and structures represented by the following general formulas (1) to (5). [Chemistry 2] [Chemistry 3] [Chemistry 4] [Chemistry 5] [Chemistry 6] In each of formulae (1) to (5), the site indicated by * is a bonding site to the oxygen atom in the general formula (I), and the site indicated by ** is a bonding site to the Rf group in the general formula (I).

4. The water- and oil-repellent agent according to claim 1, wherein The Rf group in the general formula (I) is represented by the following general formula (7) or (8), [Chemistry 7] Wherein, n is an integer from 5 to 28, [Chemistry 8] CF3-(OCF2CF2) p -(OCF2) q -OCF2- (8) In the formula, p is an integer of 0 to 41, q is an integer of 0 to 73, and is a number satisfying p+q=8 to 73. The repeating units shown in parentheses with p and q may be randomly bonded. The water- and oil-repellent according to claim 1 , which can form a film having a water contact angle of 115° or greater when applied to a glass plate. The water- and oil-repellent according to claim 1 , which can form a film having a hexadecane contact angle of 75° or greater when applied to a glass plate.

7. The water- and oil-repellent according to claim 1, which can form a film having an oil repellency of grade 7 or higher according to AATCC test method 118-2020 when applied to a substrate, and an oil repellency after heating at 150°C for 100 hours that is not lower than the initial oil repellency.

8. The water- and oil-repellent agent according to any one of claims 1 to 7, wherein The substrate of the object to be coated is a fiber or a porous membrane.

9. The water- and oil-repellent agent according to claim 8, wherein The porous membrane contains PTFE, ie, polytetrafluoroethylene.

10. An article having a coating film of the water- and oil-repellent agent according to any one of claims 1 to 7 on its surface.

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