Liquid-repellent agent composition, liquid-repellent agent treated product, and method for imparting liquid repellency

Abstract

A liquid-repellent agent composition according to the present invention includes: a polymer (A) containing a constitutional unit derived from a monomer (a) expressed by formula (1), and a constitutional unit derived from an acrylic monomer (b) that has a C6-28 alkyl group; and a liquid medium.　With the present invention, it is possible to provide: a liquid-repellent agent composition that exhibits excellent liquid repellency when used on a treated product, has good compatibility with polar solvents, and includes a non-fluorinated polymer; a liquid-repellent agent treated product that is obtained by treatment with the liquid-repellent agent composition; and a method for imparting liquid repellency that uses the liquid-repellent agent composition. (In formula (1), X represents O or a NH group, and R1 represents a C1-28 alkyl group.)

Description

Liquid repellent composition, liquid repellent-treated product, and method for imparting liquid repellency

[0001] The present invention relates to a liquid repellent composition, a liquid repellent-treated product, and a method for imparting liquid repellency.

[0002] Conventionally, surface treatment agents containing fluorine-containing compounds have been used to impart liquid repellency to fibers, leather, paper, etc. However, in recent years, concerns have arisen about the environmental impact of fluorine-containing compounds. For this reason, there has been a demand for non-fluorine-based surface treatment agents that can impart excellent liquid repellency without containing fluorine-containing compounds.

[0003] Known non-fluorine-based surface treatment agents include long-chain alkyl group-containing acrylic resins, silicone resins, and long-chain fatty acid esters.

[0004] For example, Patent Document 1 discloses that, as an acrylic resin containing a long-chain alkyl group, a non-fluorinated polymer obtained from an acrylic monomer containing a long-chain alkyl group and an acrylic monomer containing an alkylene glycol group as a hydrophilic group can impart water and oil repellency to paper, and Patent Document 2 discloses that a non-fluorinated polymer obtained from a 1,2-disubstituted ethylene monomer having a long-chain dialkyl group can impart water repellency to cloth and cotton.

[0005] Furthermore, Patent Document 3 discloses that, as a composition containing a silicone resin, a non-fluorine-based composition comprising a copolymer obtained from an ethylenic carboxylic acid ester monomer and an ethylenic carboxylic acid monomer, and a polyether-modified dimethylsiloxane can impart water and oil repellency to cloth and glass substrates.

[0006] Furthermore, Patent Document 4 discloses a composition containing a long-chain fatty acid ester, which can impart water repellency to fabrics and leather.

[0007] On the other hand, non-polar solvents such as heptane and hexane are used as solvents for liquid repellent compositions containing the above-mentioned non-fluorine-based surface treatment agents from the viewpoint of solubility and ease of application, but because the volatility is too high and application properties are reduced, a method of adding a polar solvent to reduce volatility is known (Patent Document 5). However, in the prior document, the substrate is limited to glass only, and there is a problem in that a good water-repellent coating film cannot be formed on a substrate that does not have a hydroxyl group.

[0008] International Publication No. 2020 / 054856 International Publication No. 2022 / 220198 JP 2023-22835 A JP 2024-35579 A JP 2022-96138 A

[0009] That is, an object of the present invention is to provide a liquid repellent composition containing a non-fluorinated polymer that exhibits excellent liquid repellency to a treated object and has good compatibility with polar solvents, a liquid repellent-treated object obtained by treating with the liquid repellent composition, and a method for imparting liquid repellency using the liquid repellent composition.

[0010] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have found a liquid repellent composition that can achieve the above-mentioned object, and have completed the present invention. The gist of the present invention is as follows: [1] A liquid repellent composition comprising a polymer (A) having a structural unit derived from a monomer (a) represented by the following formula (1) and a structural unit derived from an acrylic monomer (b) having an alkyl group having 6 to 28 carbon atoms, and a liquid medium: (In formula (1), X represents O or an NH group, and R １ represents an alkyl group having 1 or more and 28 or less carbon atoms.) [2] The liquid repellent composition according to the above [1], wherein the acrylic monomer (b) has a structure represented by formula (2). (In formula (2), R ２ represents a hydrogen atom or a methyl group, Z represents O or an NH group, R ３ represents a linear or branched alkyl group having 6 to 28 carbon atoms, m represents 0 or 1, and Y represents any structure selected from the group consisting of hydroxyurethane structures of the following formulas (3), (4), (5), and (6): [3] The liquid repellent composition according to [1] or [2] above, further comprising a fatty acid ester (B), the fatty acid ester (B) having a melting point of 40°C or higher and containing an alkyl group having 6 to 28 carbon atoms. [4] A liquid repellent-treated object obtained by treating with the liquid repellent composition according to any one of [1] to [3] above. [5] A method for imparting liquid repellency to an object to be treated by applying the liquid repellent composition according to any one of [1] to [3] above to the object to be treated.

[0011] According to the present invention, it is possible to provide a liquid repellent composition containing a non-fluorinated polymer that exhibits excellent liquid repellency to a treated object and has good compatibility with polar solvents, a liquid repellent-treated object obtained by treating the liquid repellent composition, and a method for imparting liquid repellency using the liquid repellent composition. Incidentally, imparting liquid repellency means imparting both water repellency and oil repellency.

[0012] In this specification, "(meth)acrylic" is a generic term that includes acrylic and methacrylic, and "(meth)acrylate" is a generic term that includes acrylate and methacrylate. Terms such as "(meth)acryloyl group" are also used as generic terms, similar to "(meth)acrylate". Hereinafter, embodiments of the present invention will be described.

[0013] [Liquid Repellent Composition] The liquid repellent composition of the present invention contains the polymer (A) and a liquid medium. Each component contained in the liquid repellent composition will be described below.

[0014] <Polymer (A)> The polymer (A) in the present invention is a polymer having a structural unit derived from a monomer (a) represented by the following formula (1) and a structural unit derived from an acrylic monomer (b) having an alkyl group having 6 to 28 carbon atoms: (In formula (1), X represents O or an NH group, and R １ represents an alkyl group having 1 to 28 carbon atoms.

[0015] The monomer (a) is a monomer represented by formula (1): In formula (1), X represents O or an NH group. From the viewpoint of liquid repellency, X is preferably O.

[0016] In formula (1), R １represents a linear or branched alkyl group having 1 to 28 carbon atoms. From the viewpoint of liquid repellency and compatibility, R １ is preferably an alkyl group having 6 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms, and even more preferably an alkyl group having 16 to 18 carbon atoms. １ The alkyl group is preferably a straight-chain alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, a lauryl group, a myristyl group, a cetyl group, a stearyl group, a behenyl group, and an isostearyl group.

[0017] The acrylic monomer (b) has an alkyl group having 6 to 28 carbon atoms. The number of carbon atoms in the alkyl group is preferably 12 to 24, and more preferably 16 to 18. The alkyl group is preferably a linear or branched hydrocarbon group, and more preferably a linear alkyl group.

[0018] The acrylic monomer (b) is preferably a monomer represented by formula (2) from the viewpoints of liquid repellency and compatibility.

[0019] In formula (2), R ２ is a hydrogen atom or a methyl group, preferably a hydrogen atom. Z is O or an NH group, preferably O from the viewpoint of compatibility. R ３ represents a linear or branched alkyl group having 6 to 28 carbon atoms. From the viewpoint of liquid repellency and compatibility, an alkyl group having 12 to 24 carbon atoms is preferred, an alkyl group having 12 to 22 carbon atoms is more preferred, and an alkyl group having 16 to 18 carbon atoms is even more preferred. ３ The alkyl group is preferably a straight chain alkyl group. Examples of the alkyl group include a lauryl group, a myristyl group, a cetyl group, a stearyl group, a behenyl group, and an isostearyl group.

[0020] m is 0 or 1, and from the viewpoint of liquid repellency and compatibility, m is preferably 1. When m is 0, Y is a single bond, and in formula (2), Z and R ３ When m is 1, Y has a structure selected from the formulas (3) to (6) described below.

[0021] In formula (2), Y is one structure selected from the group consisting of hydroxyurethane structures of formula (3), formula (4), formula (5), and formula (6). From the viewpoint of liquid repellency, the structure of formula (3) or formula (4) is particularly preferred as Y, and formula (4) is more preferred.

[0022] The carbon atom at the left end shown in the above formulas (3) to (6) is bonded to Z in formula (2), and the nitrogen atom at the right end shown in formulas (3) to (6) is bonded to R in formula (2). ３ and combine.

[0023] The method for producing the monomer represented by formula (2) is not particularly limited, and it can be produced by a known method, examples of which include lauryl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl (meth)acrylamide, icosyl (meth)acrylamide, behenyl (meth)acrylamide, etc. Also, it can be obtained by an addition reaction between a compound having both a (meth)acryloyl group and a cyclic carbonate group and an amine compound having a hydrocarbon group having 6 to 28 carbon atoms.

[0024] The acrylic monomer (b) represented by formula (2) may be a mixture of two or more types. In this case, it is preferable that at least one of the acrylic monomers (b) is used in combination with a monomer having a hydroxyurethane structure from the viewpoints of liquid repellency and compatibility.

[0025] In the polymer (A) of the present invention, the mass ratio (a) / (b) of the structural units derived from the monomer (a) to the structural units derived from the acrylic monomer (b) is in the range of 1 / 99 to 70 / 30. From the viewpoint of liquid repellency and compatibility, the mass ratio (a) / (b) is preferably 10 / 90 to 50 / 50, and more preferably 15 / 85 to 30 / 70. When the mass of the structural units derived from the monomer (a) is smaller than the range of 70 / 30, liquid repellency tends to be improved.

[0026] The content of the polymer (A) in the liquid repellent composition is not particularly limited, but is preferably 0.1 to 50 mass %, and more preferably 1 to 20 mass %, when the total amount of the liquid repellent composition is 100 mass %.

[0027] <Method for producing polymer (A)> The polymer (A) can be obtained by radical polymerization of a mixture containing at least one monomer (a) and at least one acrylic monomer (b) having an alkyl group having 6 to 28 carbon atoms. The polymerization method is not particularly limited, and known polymerization methods such as solution polymerization, emulsion polymerization, and suspension polymerization can be used.

[0028] As the polymerization initiator, an organic peroxide, an azo compound, a persulfate, etc. can be used. Specific examples of the polymerization initiator include tert-butyl peroxypivalate, tert-hexylperoxyneodecanate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di-3,5,5-trimethylhexanoyl peroxide, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, ammonium persulfate, etc. The amount of the polymerization initiator used can be appropriately set depending on the combination of monomers used, reaction conditions, etc.

[0029] In the solution polymerization method, various monomers are dissolved in any solvent in the presence of a polymerization initiator, and after replacing the atmosphere with nitrogen, the mixture is heated and stirred to polymerize.

[0030] In the emulsion polymerization method, various monomers are emulsified in water or a mixture of an organic solvent and water in the presence of a polymerization initiator and a surfactant, and the mixture is heated and stirred after nitrogen substitution. Alternatively, the polymerization can be carried out by adding water after polymerization (solution polymerization or emulsion polymerization), removing the solvent, and dispersing the polymer in water.

[0031] The arrangement of the constituent units of the monomers in the polymer (A) is not particularly limited, and may be random, block, graft, or the like.

[0032] The weight-average molecular weight of polymer (A) is preferably 5,000 to 2,000,000. From the viewpoint of liquid repellency and compatibility, the weight-average molecular weight of polymer (A) is more preferably 8,000 to 1,900,000, even more preferably 10,000 to 500,000, and even more preferably 15,000 to 200,000. If the weight-average molecular weight is within this range, the uniformity of the polymer coating is improved, and the liquid repellency is improved. The weight-average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0033] A chain transfer agent may be used during polymerization of the polymer (A) for the purpose of adjusting the molecular weight. Examples of the chain transfer agent include lauryl mercaptan and tert-butyl alcohol. The amount of the chain transfer agent used can be appropriately determined depending on the combination of monomers used, reaction conditions, etc.

[0034] <Liquid Medium> The liquid repellent composition of the present invention contains a liquid medium. By including a liquid medium, it is possible to facilitate adhesion of the liquid repellent composition to the object to be treated.

[0035] The liquid medium is not particularly limited as long as it dissolves or disperses the polymer, and examples thereof include water, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, n-propanol, isopropyl alcohol, ethyl acetate, butyl acetate, tetrahydrofuran, dimethylformamide, toluene, xylene, n-hexane, isohexane, n-heptane, cyclopentane, cyclohexane, methylcyclohexane, and isoparaffin-based solvents. These liquid media can be appropriately selected depending on the type of substrate (cloth, leather, etc.) and the manufacturing method (spray coating, immersion coating, etc.). In particular, for applications requiring volatility of the liquid solvent, hydrocarbon-based solvents are preferred in terms of preventing deterioration and maintaining the texture of the substrate, and aliphatic hydrocarbon-based solvents are preferred. More preferred are n-hexane, isohexane, n-heptane, cyclopentane, cyclohexane, and methylcyclohexane, with n-hexane, n-heptane, and cyclohexane being particularly preferred. These liquid media may be used alone or in combination of two or more.

[0036] The content of the liquid medium in the liquid repellent composition is not particularly limited, but is preferably 50 to 99.9% by mass, and more preferably 80 to 99% by mass, when the total amount of the liquid repellent composition is 100% by mass.

[0037] In the present invention, it is preferable that the volatile solvent used as the liquid medium further contains a polar solvent. Under high temperature conditions, such as in summer, the volatile solvent evaporates in a short period of time, which deteriorates the coatability and reduces the liquid repellency. Therefore, by including one or more polar solvents with a boiling point of 150°C or higher under normal pressure, the coatability can be improved and the reduction in liquid repellency can be suppressed. Here, the volatile solvent refers to a solvent with a boiling point of 100°C or lower, and examples thereof include n-hexane (68°C), isohexane (62°C), n-heptane (98°C), n-hexane (68°C), cyclopentane (50°C), cyclohexane (81°C), and methylcyclohexane (100°C).

[0038] The polar solvent is not particularly limited, but examples thereof include ketones such as diisobutyl ketone, esters such as propylene glycol monomethyl ether propionate, alcohols such as benzyl alcohol, glycols such as ethylene glycol and propylene glycol, glycol ethers such as propylene glycol monomethyl ether and dipropylene glycol monomethyl ether, etc. The amount of polar solvent added is preferably 1 to 10% by mass based on the total amount of the liquid medium from the viewpoints of coatability and volatility.

[0039] <Fatty Acid Ester (B)> The liquid repellent composition of the present invention preferably contains a fatty acid ester (B) in addition to the polymer (A) and the liquid medium. Adding the fatty acid ester (B) can further improve liquid repellency. From the viewpoint of improving liquid repellency, the fatty acid ester (B) preferably has a melting point of 40°C or higher and contains an alkyl group having 6 to 28 carbon atoms. From the viewpoint of liquid repellency, the fatty acid ester (B) more preferably has an alkyl group having 12 to 24 carbon atoms, more preferably has an alkyl group having 12 to 22 carbon atoms, and even more preferably has an alkyl group having 16 to 18 carbon atoms. The fatty acid ester (B) is not particularly limited, but can be obtained, for example, by esterification using a fatty acid having 6 to 28 carbon atoms and an alcohol. From the viewpoint of liquid repellency, the fatty acid having 6 to 28 carbon atoms is preferably a fatty acid having 12 to 22 carbon atoms, and more preferably a fatty acid having 16 to 18 carbon atoms. The alcohol is not particularly limited, but preferably has 6 to 28 carbon atoms, more preferably 2 to 24, even more preferably 2 to 18, particularly preferably 2 to 10, and most preferably 2 to 5. Examples of the alkyl group contained in the fatty acid ester (B) include a lauryl group, a myristyl group, a cetyl group, a stearyl group, and a behenyl group. As the alkyl group, the fatty acid ester (B) may have one or more alkyl groups per molecule. From the viewpoints of liquid repellency and compatibility with polar solvents, a di-form having two alkyl groups per molecule, a tri-form having three alkyl groups per molecule, or a tetra-form having four alkyl groups per molecule is preferred, with the di-form being more preferred.

[0040] The melting point of the fatty acid ester (B) is 40° C. or higher, and from the viewpoint of liquid repellency and compatibility, preferably 45° C. to 80° C. The melting point of the fatty acid ester (B) in the present invention is a melting point measured in accordance with the Standard Methods for the Analysis of Fats, Oils and Related Materials (compiled by the Japan Oil Chemists' Society, 2.2.4.2 Melting Point (Slip Melting Point)).

[0041] Specific examples of the fatty acid ester (B) include myristyl myristate, stearyl stearate, behenyl behenate, pentaerythritol distearate, pentaerythritol tetrastearate, polyoxyethylene monostearate, ethylene glycol distearate, and polyethylene glycol distearate. From the viewpoint of liquid repellency, stearyl stearate, pentaerythritol distearate, pentaerythritol tetrastearate, and ethylene glycol distearate are preferred, with pentaerythritol distearate being more preferred. These components may be used alone or in combination of two or more.

[0042] In the liquid repellent composition, when the total content of the polymer (A) and the fatty acid ester (B) is taken as 100 parts by mass, the mass ratio of the polymer (A) to the fatty acid ester (B) ((A) / (B)) is preferably 50 / 50 to 99 / 1. From the viewpoints of liquid repellency and compatibility, the range of 70 / 30 to 95 / 5 is more preferable, and 80 / 20 to 95 / 5 is even more preferable.

[0043] The liquid repellent composition of the present invention can be produced by mixing the polymer (A) of the present invention, a liquid medium, and the fatty acid ester (B) which is blended as needed.

[0044] <Additives> In addition to the polymer (A) and the liquid medium, the liquid repellent composition of the present invention may further contain additives within a range that does not impair the effects of the present invention. For example, when the total amount of the polymer and the liquid medium is 100 parts by mass, the content of the additive is preferably 10 parts by mass or less.

[0045] Examples of such additives include polymers other than the polymer (A) that can impart liquid repellency, crosslinking agents, antibacterial and deodorizing agents, flame retardants, antistatic agents, softeners, and wrinkle inhibitors. In particular, when treating fabrics, clothing, and the like, it is preferable to add a crosslinking agent to prevent a decrease in water repellency due to washing. Examples of crosslinking agents include compounds having at least one of methylol melamine, an isocyanate group, and a blocked isocyanate group. By attaching a crosslinking agent to the object to be treated and then subjecting the object to heat treatment, the liquid repellency can be maintained even after washing.

[0046] <Liquid-Repellent-Treated Articles> The liquid-repellent composition containing the polymer (A) of the present invention can be used to impart liquid repellency to an article to be treated, thereby producing a liquid-repellent-treated article. That is, the present invention can also provide an article to be treated with the liquid-repellent composition. Examples of applicable articles to be treated include natural fibers such as cotton, linen, and silk; recycled fibers such as rayon and cupra; semi-synthetic fibers such as acetate and triacetate; synthetic fibers such as polyamide, polyester, polyacrylonitrile, polypropylene, polyvinyl chloride, and polyvinyl alcohol; natural leather; synthetic leather; fur; paper; wood; blends of these fibers and fabrics, clothing, and shoes made from these fibers; glass fiber; glass; brick; cement; metal; and plastic. Among these, the liquid-repellent composition is particularly effective on paper, synthetic fibers, natural fibers, natural leather, and glass.

[0047] The water repellent composition of the present invention can be applied by a common method such as spray coating, bar coating, or dip coating. After applying the water repellent composition of the present invention to the object to be treated, it is preferable to dry the object by volatilizing the liquid medium at room temperature or by heat treatment or the like. There are no particular restrictions on the temperature conditions during drying, but taking into consideration thermal deterioration of the object to be treated, it is preferable that the temperature be, for example, 10 to 200°C, and preferably 30 to 150°C.

[0048] Hereinafter, the embodiments of the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0049] Table 1 shows the monomers (a) [a-1 to a-4] represented by formula (1) which were used as raw materials for the polymers in the examples, and a'-1 to a'-3 which were used as raw materials for the polymers in the comparative examples. Table 2 shows the acrylic monomers (b) [b-1 to b-4] represented by formula (2) which were used as raw materials for the polymers in the examples, and b'-1 which was used as raw material for the polymers in the comparative examples. Table 3 shows the fatty acid esters (B) used in the examples.

[0050]

[0051]

[0052]

[0053] (Synthesis of Polymer A-1) 140 g of methylcyclohexane was charged into a 500 mL four-neck flask equipped with a condenser, the flask was purged with nitrogen, and the reaction vessel was heated to 55°C. Next, a polymerization initiator solution consisting of 20.2 g of monomer (a-1), 60.5 g of monomer (b-1), 2.5 g of tert-hexyl peroxyneodecanate, and 25 g of methylcyclohexane was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was reacted at 55°C for 4 hours, then the temperature was raised to 70°C and further reacted for 2 hours to obtain a solution containing a polymer. Table 3 shows the blend amounts (parts by mass) of monomers (a-1) and (b-1) and the weight average molecular weight (unit: 10,000) of the resulting polymer.

[0054] (Polymers A-2 to A-11, A'-1 to A'-6) Each polymer was obtained in the same manner as for Polymer A-1, except that the raw materials were added in amounts such that the respective components were used in the blending ratios shown in Table 4 (the units of blending amounts in the table are parts by mass).

[0055] (Measurement of Weight-Average Molecular Weight) The weight-average molecular weight of polymers A-1 to A-11 and A'-1 to A'-6 was determined using gel permeation chromatography (GPC) under the following conditions: Apparatus: HLC-8220 manufactured by Tosoh Corporation Column: LF-804 manufactured by Shodex Standard substance: polystyrene Eluent: THF (tetrahydrofuran) Flow rate: 1.0 mL / min Column temperature: 40°C Detector: RID (differential refractive index detector)

[0056]

[0057] Example 1 <Evaluation of Liquid Repellency and Compatibility> The liquid repellency of polymer A-1 was evaluated by the following static contact angle evaluation, shower test, and oil repellency evaluation. In addition, the compatibility was evaluated by the following solubility test.

[0058] <Static Contact Angle Evaluation> The above polymer A-1 was diluted with methylcyclohexane as a liquid medium to prepare a solution (liquid repellent composition) with a polymer concentration of 10% by mass. Next, 1 g of the liquid repellent composition was applied to a glass plate using a bar coater (RDS 32) and dried on a hot plate at 80°C for 1 hour to prepare a test piece (liquid repellent-treated product). The static contact angles of the obtained test piece with water and hexadecane were measured using a contact angle meter (DM701, manufactured by Kyowa Interface Science Co., Ltd.). According to the following criteria, a score of B or higher was considered to be acceptable. Static contact angle of water: A: 105° or higher; B: 80 to 104°; C: 79° or less; Static contact angle of hexadecane: A: 40° or higher; B: 30 to 39°; C: 29° or less

[0059] <Shower Test> The above polymer A-1 was diluted with methylcyclohexane as a liquid medium to prepare a solution (liquid repellent composition) with a polymer concentration of 10% by mass. Next, 5 g of the liquid repellent composition was applied to cowhide by spraying the solution using a spray gun, and the resultant was dried at room temperature for 1 hour to prepare a test piece (liquid repellent-treated product). The test piece was then attached to a spray tester AW-5 (manufactured by Intec Co., Ltd.) in accordance with JIS L 1092, and 250 mL of water was sprayed on it. The wetness of the test piece after spraying was evaluated on a scale of 1 to 5. The higher the grade, the better the water repellency. Grade 3 or higher was considered a pass value. Grade 5: No wetness or water droplets on the surface Grade 4: Slight water droplets on the surface Grade 3: Partial wetness on the surface Grade 2: Wetness on half the surface Grade 1: Wetness on the entire surface

[0060] <Oil repellency evaluation> Using the cowhide test pieces prepared in the shower test, the oil repellency was evaluated on the following scale of 0 to 5 based on the AATCC (American Association of Textile Chemists and Colorists) 118 method. The higher the scale, the better the oil repellency. Grades 2 and above were considered acceptable. Grade 5: n-dodecane Grade 4: n-tetradecane Grade 3: n-hexadecane Grade 2: liquid paraffin / n-hexadecane = 65 / 35 parts by mass Grade 1: liquid paraffin Grade 0: absorbed into liquid paraffin

[0061] <Evaluation of Compatibility by Solubility Test> The polar solvents shown in the table were added to a polymer solution (a solution diluted with methylcyclohexane to a polymer concentration of 20% by mass) at 1, 3, and 5% by mass relative to the polymer solution, and the solution was thoroughly stirred. After 1 hour, the solution was visually observed to check for the presence or absence of precipitates, and the results were evaluated as follows, with B or higher being considered pass. A: No precipitates at 5% by mass B: No precipitates at 3% by mass C: No precipitates at 1% by mass D: Presence of precipitates at 1% by mass

[0062] Examples 2 to 11, Comparative Examples 1 to 6 Evaluations were carried out in the same manner as in Example 1, except that the polymers shown in Tables 5 and 6 were used.

[0063] Examples 12 to 14 Each evaluation was performed in the same manner as in Example 1, except that B-1 (pentaerythritol distearate (melting point 53°C)) as a fatty acid ester was further added to Polymer A shown in Table 5 in the mass ratio shown in Table 5.

[0064] (Example 15) Each evaluation was performed in the same manner as in Example 1, except that B-2 (ethylene glycol distearate (melting point 63°C)) as a fatty acid ester was further added to Polymer A shown in Table 5 in the mass ratio shown in Table 5.

[0065] Comparative Example 7 Each evaluation was carried out in the same manner as in Example 1, except that only fatty acid ester B-1 was added instead of polymer A.

[0066]

[0067]

[0068] As is clear from the results in Table 5, Examples 1 to 15 exhibited good liquid repellency and compatibility. On the other hand, as shown in Table 6, Comparative Examples 1 and 2 did not contain the structure derived from monomer (a), and therefore had poor liquid repellency and compatibility. Comparative Example 3, in which benzylmaleimide was used instead of monomer (a), had poor liquid repellency. Comparative Example 4, in which the structure derived from monomer (b) was not contained, had poor liquid repellency. Comparative Examples 5 and 6, in which the structure derived from monomer (a) was not contained, had poor liquid repellency and compatibility. Comparative Example 7, in which copolymer (A) was not contained, had poor liquid repellency and compatibility.

Claims

1. A liquid repellent composition comprising a polymer (A) having a structural unit derived from a monomer (a) represented by the following formula (1) and a structural unit derived from an acrylic monomer (b) having an alkyl group having 6 to 28 carbon atoms, and a liquid medium: (In formula (1), X represents O or an NH group, and R １ represents an alkyl group having 1 to 28 carbon atoms.

2. The liquid repellent composition according to claim 1, wherein the acrylic monomer (b) has a structure represented by formula (2). (In formula (2), R ２ represents a hydrogen atom or a methyl group, Z represents O or an NH group, R ３ represents a linear or branched alkyl group having 6 to 28 carbon atoms, m represents 0 or 1, and Y represents any structure selected from the group consisting of hydroxyurethane structures of the following formulas (3), (4), (5), and (6):

3. The liquid repellent composition according to claim 1, further comprising a fatty acid ester (B), said fatty acid ester (B) having a melting point of 40°C or higher and containing an alkyl group having 6 to 28 carbon atoms.

4. A liquid-repellent treated object obtained by treating with the liquid-repellent composition according to any one of claims 1 to 3.

5. A method for imparting liquid repellency to an object to be treated by applying the liquid repellent composition according to any one of claims 1 to 3 to the object to be treated.

Images