Surface treatment agent and article using same

Abstract

Disclosed is a surface treatment agent containing a polymer that contains, as a monomer component, an acrylate monomer in which acryloyl groups or alpha-substituted acryloyl groups are bonded to two or three C10-40 monovalent aliphatic hydrocarbon groups via trivalent or tetravalent linking groups, and the two or three C10-40 monovalent aliphatic hydrocarbon groups are bonded to the same atom in the trivalent or tetravalent linking group. This surface treatment agent imparts good water- and oil-repellency without containing perfluoroalkyl groups, which pose a particular concern in terms of environmental impact, in the molecular chain. Also disclosed is an article having a coating film of the surface treatment agent on the surface.

Description

Surface treatment agents and articles using the same 【0001】 The present invention relates to a surface treatment agent that imparts water-repellent and oil-repellent properties to a substrate and an article using the same, and more particularly to a surface treatment agent that does not contain perfluoroalkyl groups in its molecular chain, which are a concern for environmental impact, and further comprises a non-fluorine polymer as an active ingredient, which is an acrylate monomer having two or more hydrocarbon groups in its molecular chain, and an article having a coating of the surface treatment agent on its surface. 【0002】 Conventionally, fluorine-based surface treatment agents containing fluorine compounds have been applied to substrates to provide surface modification functions such as water and oil repellency. Such fluorine-based surface treatment agents are generally manufactured by polymerizing or copolymerizing monomers having fluoroalkyl groups. Although products treated with fluorine-based surface treatment agents exhibit excellent water and oil repellency, monomers having fluoroalkyl groups raise environmental concerns. Therefore, there has been an international demand for non-fluorine-based surface treatment agents that do not contain fluorine compounds but exhibit high-performance water and oil repellency comparable to that of fluorine-based surface treatment agents. 【0003】 Conventionally, research has been conducted on surface treatment agents that do not contain fluorine compounds, and known non-fluorine surface treatment agents include long-chain acrylic resins having linear or branched aliphatic hydrocarbon groups. For example, Patent Document 1 discloses a surface treatment agent for a non-fluorine copolymer having repeating units derived from an acrylate monomer having a long-chain aliphatic hydrocarbon group and an acrylate monomer having a cyclic hydrocarbon group. Patent Document 2 discloses a surface treatment agent for a non-fluorine copolymer having repeating units derived from an acrylate monomer having a long-chain aliphatic hydrocarbon group and a halogenated olefin monomer. 【0004】 Furthermore, as a fiber treatment composition that does not contain fluorine compounds, Patent Document 3 discloses a composition that includes at least one isocyanate-reactive oligomer and at least one polyisocyanate as essential components. 【0005】 However, none of them have been sufficiently demonstrated to be effective, especially in terms of oil repellency. 【0006】Japanese Patent Publication No. 2015-120894, Japanese Patent Publication No. 2017-165872, Japanese Patent Publication No. 2018-510234 【0007】 The present invention has been made in view of the above circumstances, and aims to provide a surface treatment agent comprising a non-fluorine polymer with acrylate monomers as monomer units as an active ingredient, which provides excellent water-repellent and oil-repellent properties despite not containing perfluoroalkyl groups in its molecular chain, which are of particular concern regarding environmental impact, and an article having a coating of the surface treatment agent on its surface. 【0008】 As a result of diligent research to solve the above objectives, the present inventors have found that when a non-fluorinated monomer has two or three long-chain aliphatic hydrocarbon groups on the same atom, a surface treatment agent containing a polymer having such monomer units exhibits good water and oil repellency even without containing a fluorine component, thus completing the present invention. 【0009】 Accordingly, the present invention provides the following surface treatment agents and articles using the same. [1] A non-fluorine surface treatment agent for imparting water-repellent and oil-repellent properties to a substrate surface, comprising a polymer in which an acrylate monomer is a monomer component, wherein an acryloyl group or an α-substituted acryloyl group and two or three monovalent aliphatic hydrocarbon groups having 10 to 40 carbon atoms are bonded via a trivalent or tetravalent linking group, and the two or three monovalent aliphatic hydrocarbon groups having 10 to 40 carbon atoms are bonded to the same atom in the trivalent or tetravalent linking group. [2] The surface treatment agent according to [1], wherein the two or three monovalent aliphatic hydrocarbon groups are the same. [3] The acrylate monomer having the following general formula (I) A surface treatment agent according to [1] or [2], wherein the monomer is represented by the formula [wherein X is a hydrogen atom, a halogen atom, an alkyl group or an aryl group; Y is a single bond, or a divalent hydrocarbon group having 1 to 10 carbon atoms that may contain one or more selected from the group consisting of an oxygen atom, -NR'- (where R' is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), an amide bond, a urethane bond and a urea bond; Z is a carbon atom, nitrogen atom or silicon atom to which R is bonded, or a trivalent or tetravalent linking group containing the carbon atom, nitrogen atom or silicon atom; R is a monovalent hydrocarbon group having 10 to 40 carbon atoms; and n is 2 or 3. All Rs are bonded to the same atom of carbon, nitrogen atom or silicon atom in Z.]. [4] A surface treatment agent according to [3], wherein X in general formula (I) is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, or a phenyl group. [5] The surface treatment agent according to [3] or [4], wherein the trivalent or tetravalent linking group of Z in general formula (I) is a carbon atom, a nitrogen atom, a silyl group, a silyl ether group, or a group represented by the following formula (1). [6] The surface treatment agent according to [5], wherein the trivalent or tetravalent linking group of Z in general formula (I) is a carbon atom, a nitrogen atom, or a group represented by the following formula (1). [7] A surface treatment agent according to any one of [1] to [6] that provides a coating on a glass plate with a water contact angle of 100° or more when applied. [8] A surface treatment agent according to any one of [1] to [7] that provides a coating on a glass plate with a hexadecane contact angle of 35° or more when applied. [9] An article having a coating of the surface treatment agent according to any one of [1] to [8] on its surface. 【0010】 According to the present invention, it is possible to provide a surface treatment agent comprising a non-fluorine polymer with acrylate monomers as monomer units as an active ingredient, which provides good water-repellent and oil-repellent properties to the substrate surface without containing perfluoroalkyl groups in the molecular chain, which are of particular concern regarding environmental impact, and an article having a coating film of the surface treatment agent on its surface. 【0011】The surface treatment agent of the present invention contains a polymer in which an acrylate monomer is used as one monomer component, wherein an acryloyl group or an α-substituted acryloyl group and two or three monovalent aliphatic hydrocarbon groups having 10 to 40 carbon atoms are bonded via a trivalent or tetravalent linking group, and the two or three monovalent aliphatic hydrocarbon groups having 10 to 40 carbon atoms are bonded to the same atom in the trivalent or tetravalent linking group, and the polymer does not contain a fluorine atom. 【0012】 In the present invention, "acrylate monomer" is a general term for compounds having an acryloyl (hereinafter also called acrylic) group or an α-substituted acryloyl (hereinafter also called α-substituted acrylic) group, and also includes compounds in which two or more acrylic groups or α-substituted acrylic groups are introduced to the side chains or terminals of various polymers by any method. 【0013】 In the above-mentioned acrylate monomer, it is preferable that two or three of its monovalent aliphatic hydrocarbons are the same. 【0014】 The above acrylate monomer is preferably one represented by the following general formula (I). [In the formula, X is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; Y is a single bond, or a divalent hydrocarbon group having 1 to 10 carbon atoms that may contain one or more selected from the group consisting of an oxygen atom, -NR'- (where R' is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), an amide bond, a urethane bond, and a urea bond; Z is a trivalent or tetravalent linking group containing a carbon atom, nitrogen atom, or silicon atom to which R is bonded; R is a monovalent hydrocarbon group having 10 to 40 carbon atoms; and n is 2 or 3. Note that all Rs are bonded to the same carbon atom, nitrogen atom, or silicon atom in Z.] 【0015】 Here, X in general formula (I) is a hydrogen atom, a halogen atom (particularly a chlorine atom, a bromine atom, or an iodine atom), an alkyl group, or an aryl group (particularly a phenyl group), and preferably a methyl group or a hydrogen atom. 【0016】In general formula (I), Y is a divalent hydrocarbon group having 1 to 10 carbon atoms, which may contain one or more selected from the group consisting of a single bond, an oxygen atom, -NR'- (where R' is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), an amide bond, a urethane bond, and a urea bond. Preferably, a combination of an alkylene group (particularly an ethylene group) and an amide bond or a urethane bond is included, as this allows for easy introduction, improved solubility, and orientation of the hydrocarbon group due to interactions between side chains. 【0017】 Furthermore, Z in general formula (I) is a carbon atom, nitrogen atom, or silicon atom to which multiple monovalent aliphatic hydrocarbon groups (R) are bonded, or a trivalent or tetravalent linking group containing such carbon atom, nitrogen atom, or silicon atom. Preferably, since it is easy to introduce two or three monovalent aliphatic hydrocarbon groups, examples include a carbon atom, nitrogen atom, silyl group, silyl ether group, or a group represented by the following formula (1). Particularly preferred are a carbon atom, nitrogen atom, or a group represented by the following formula (1). 【0018】 In general formula (I), R is a monovalent aliphatic hydrocarbon group having 10 to 40 carbon atoms, preferably a monovalent aliphatic hydrocarbon group having 10 to 40 carbon atoms, and more preferably a monovalent saturated aliphatic hydrocarbon group having 15 to 30 carbon atoms. If R has fewer than 10 carbon atoms, the water- and oil-repellent properties decrease, and if it has more than 40 carbon atoms, the solubility in solvents decreases, making it difficult to handle. 【0019】 Examples of acrylate monomers represented by the above general formula (I) include those listed below. 【0020】 The polymer according to the present invention can be obtained by polymerizing monomer components represented by general formula (I) in a solvent using a known method such as solution polymerization with a radical polymerization initiator. 【0021】The polymer may have structural units derived from polymerizable carbon-carbon double bond-containing monomers other than the acrylate monomers described above, in which two or three monovalent aliphatic hydrocarbon groups having 10 to 40 carbon atoms are bonded to the same atom in a trivalent or tetravalent linking group. 【0022】 The structural units derived from the polymerizable carbon-carbon double bond-containing monomer can be included in an amount that does not impair the effects of the present invention, and improvements in properties such as polymerizability and solubility, in addition to water-repellent and oil-repellent properties, can be expected. 【0023】 Specific examples of the polymerizable carbon-carbon double bond-containing monomers include, in addition to the acrylate monomers mentioned above in which two or three monovalent aliphatic hydrocarbon groups having 10 to 40 carbon atoms are bonded to the same atom in a trivalent or tetravalent linking group, acrylic acid esters; monocarboxylic acids such as acrylic acid; dicarboxylic acids such as itaconic acid and maleic acid, their half-esters (monoesters), their diesters, and their acid anhydrides; styrenes such as styrene and α-methylstyrene; and vinyl esters such as vinyl acetate and vinyl propionate. 【0024】 To improve the adhesion of the surface treatment agent to the substrate, the polymerizable carbon-carbon double bond-containing monomer may have a reactive functional group, such as a hydroxyl group, carboxyl group, or amino group. 【0025】The solvent used in the polymer production method according to the present invention is preferably a solvent that can dissolve the monomer component represented by general formula (I) and does not react with the monomer component. Examples include hydrocarbon solvents [petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.)], ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), and ester solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate). Among these, tetrahydrofuran is preferred from the viewpoint of solubility. The amount of solvent used is not particularly limited, but it is preferably 50 to 2,000 parts by mass, particularly 100 to 1,000 parts by mass, and even more preferably 150 to 400 parts by mass, per 100 parts by mass of the monomer represented by general formula (I). 【0026】Radical polymerization initiators that can be used in the polymer production method according to the present invention include, for example, dimethyl azobisisobutyrate, cumene hydroperoxide, succinate peroxide, di-t-butyl peroxide, diisobutyryl peroxide, diisobutyl peroxydicarbonate, dicumyl peroxide, cyclohexanone peroxide, dimethyl-2,2'-azobisisobutyrate, benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, 2,2'-azobis(2-methylamidooxime) dihydrochloride, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutylamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], and Examples include azo compounds such as bisulfate, 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-cumylperoxide, t-butylperoxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxyisopropyl carbonate, t-butylhydroperoxide, α,α'-bis(t-butylperoxy)-p-diisopropylbenzene, organic peroxides, potassium persulfate, sodium persulfate, and ammonium persulfate. These radical polymerization initiators may be used individually or in combination of two or more types. The amount of radical polymerization initiator used is not particularly limited, but it is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of monomer represented by general formula (I). 【0027】 The polymerization conditions for the monomer represented by general formula (I) in the polymerization method using the above solvent and radical polymerization initiator are preferably 40 to 100°C, particularly 50 to 70°C, under an inert gas atmosphere for 4 to 30 hours, and especially 18 to 24 hours. 【0028】The weight-average molecular weight (Mw) of the polymer obtained in this way is preferably about 2,000 to 2,000,000, more preferably 5,000 to 500,000, even more preferably 5,000 or more and less than 20,000, and particularly preferably 8,000 or more and less than 20,000. In particular, if the weight-average molecular weight is less than 5,000, the water-repellent and oil-repellent properties when coated on a substrate may be low, and if it exceeds 500,000, the workability during coating may deteriorate. The weight-average molecular weight can be measured by high-performance liquid chromatography-mass spectrometry using tetrahydrofuran as the solvent. 【0029】 The surface treatment agent of the present invention contains a polymer of a monomer (acrylate monomer) represented by the general formula (I) described above. The surface treatment agent of the present invention is usually provided as a solvent solution of the polymer. Here, the amount of polymer in the solvent solution (concentration of polymer) is preferably 1 to 50% by mass, particularly 2 to 30% by mass, and especially 3 to 15% by mass. 【0030】 The solvent used in the surface treatment agent is not particularly limited as long as it can dissolve the polymer, but a non-fluorinated organic solvent is preferred. Examples of non-fluorinated organic solvents include tetrahydrofuran, ethylcyclohexane, and butyl acetate. Among these, tetrahydrofuran is preferable from the viewpoint of solubility. The solvent used in the polymer manufacturing method may be used as the solvent in the surface treatment agent, or additional solvent may be added after the polymer is manufactured to adjust the polymer concentration. 【0031】 The application method for the surface treatment agent of the present invention to a substrate can be, for example, a spin coating method, a dip coating method, a spray method, a roll coating method, a meniscus coating method, or a screen printing method. 【0032】The surface treatment agent of the present invention can easily form a film on the surface of a substrate such as glass, fiber, or porous membrane by drying the solvent after application to the substrate. Specifically, it is preferable to dry it at room temperature (25°C ± 10°C) for 30 minutes to 24 hours. In order to speed up the drying, heating may be performed at, for example, 40 to 150°C for about 30 seconds to 24 hours, within a range that does not affect the substrate. This film exhibits excellent water and oil repellency because the polymer contains long-chain aliphatic hydrocarbon groups. Therefore, it can be used as a water and oil repellent coating agent for glass, fiber, porous membrane, and especially fiber and porous membrane. 【0033】 Examples of fibrous substrates to which the surface treatment agent of the present invention is applied include fibers, yarns, and cloths. Examples of fibers constituting the fibrous substrate include glass fibers, carbon fibers, aramid fibers, polyethylene fibers, polytetrafluoroethylene (PTFE) fibers, Zylon fibers, boron fibers, basalt fibers, metal fibers, polyamide fibers, silicon carbide fibers, polyester fibers, ceramic fibers, alumina fibers, mineral fibers, rock fibers, slug fibers, polyoxymethylene fibers, aromatic polyamide fibers, poly(p-phenylenebenzobisoxazole) fibers, plant fibers, cellulose fibers, and lignin fibers. These fibers may be used individually or in combination of two or more types. Examples of porous membrane substrates to which the surface treatment agent of the present invention is applied include nonwoven fabrics, perforated membranes, microporous membranes, and porous bodies. Examples of materials constituting the porous membrane substrate include resins such as PTFE (polytetrafluoroethylene), ceramics, and metals, with PTFE (polytetrafluoroethylene) being preferred. 【0034】 The thickness of the coating is appropriately selected depending on the type of substrate, but for example, it may be 0.005 to 100 μm, preferably 0.01 to 10 μm, and more preferably 0.05 to 5 μm. 【0035】The film thickness can also be measured by a thin film thickness measuring device based on the optical interference method (an optical interference type film thickness meter, a reflection spectroscopic film thickness meter), a thin film thickness measuring device based on spectroscopic ellipsometry (a spectroscopic ellipsometer), etc. For example, a spectroscopic ellipsometer (manufactured by J.A. Woollam Co., Ltd., M-2000) can be used. 【0036】 Examples of the article having the coating film of the surface treatment agent of the present invention on the surface include in-vehicle products, textile products, non-woven fabrics, filtration materials used in the presence of an organic solvent liquid or its vapor, and the like. 【0037】 The contact angle with respect to water (water contact angle) of the coating film formed by applying the surface treatment agent of the present invention to a glass plate at a temperature of 25°C and a relative humidity of 40% is preferably 100° or more, particularly preferably 105° or more. In the present invention, the contact angle with respect to water is a value measured under the conditions of a droplet: 2 μl using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd., DMo-701SA). 【0038】 The contact angle with respect to hexadecane (hexadecane (HD) contact angle) of the coating film formed by applying the surface treatment agent of the present invention to a glass plate at a temperature of 25°C and a relative humidity of 40% is preferably 35° or more, particularly preferably 40° or more. In the present invention, the contact angle with respect to hexadecane is a value measured under the conditions of a droplet: 2 μL using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd., DMo-701SA). 【0039】Hereinafter, synthesis examples, examples, and comparative examples will be shown to specifically describe the present invention, but the present invention is not limited to the following examples. In the following examples, "parts" indicates parts by mass. The weight average molecular weight of the polymer was measured by high performance liquid chromatography analysis. The equipment used, measurement conditions, etc. are shown below. [Equipment used] Liquid delivery pump: Tosoh HLC-8320GPC Column oven: Tosoh HLC-8320GPC Detector: RI detector [differential refractometer] [Column conditions] Column: Tosoh TSK-GEL Super MultiporeHZ-M×2 Mobile phase [moving layer]: Kanto Chemical tetrahydrofuran (for high performance liquid chromatography) Column oven temperature: 40°C Pump oven temperature: 40°C Liquid delivery rate: 0.250 mL / min [Sample conditions] Sample concentration: 0.5 mass% Injection volume: 10 μL [Detection conditions] Detection temperature: 40°C 【0040】 [Synthesis Example 1] Synthesis of Compound (A) In a 2 L four-necked flask equipped with a thermometer, a nitrogen gas inlet, a reflux condenser, and a stirrer, 200.0 g (0.383 mol) of the compound represented by the following formula (a) 59.5 g (0.422 mol) of 2-isocyanatoethyl acrylate, 0.1 g of 4-methoxyphenol, and 1000.0 g of tetrahydrofuran (ultra-dehydrated, stabilizer-free) were mixed and aged at 40°C for 2 hours. Then, the solvent and unreacted substances were distilled off under reduced pressure to obtain 234.0 g of the product. 【0041】 The obtained product was 1 confirmed to be a compound represented by the following formula (A) by 1H-NMR. 【0042】 【0043】[Synthesis Example 2] Synthesis of Compound (B) 248.0 g of the product was obtained in the same manner as in Synthesis Example 1, except that 65.5 g (0.422 mol) of 2-isocyanatoethyl methacrylate was used instead of 59.5 g (0.422 mol) of 2-isocyanatoethyl acrylate. 【0044】 The resulting product is 1 ¹H-NMR confirmed that the compound is represented by the following formula (B). 【0045】 【0046】 [Synthesis Example 3] Synthesis of compound (c-2) A 5 L four-necked flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, and stirrer was prepared using the following formula (c-1) 150.0 g (0.296 mol) of the compound represented by [formula], 1500.0 g of tetrahydrofuran, and 22.5 g (3.94 mol) of sodium borohydride were mixed. Then, 300.0 g of methanol was added to the system, and the mixture was stirred at 60°C for 2 hours under a nitrogen atmosphere. The reaction was then stopped with hydrochloric acid, and the solvent and unreacted substances were removed by washing with water and distillation under reduced pressure to obtain 131.1 g of product. 【0047】 The resulting product is 1 ¹H-NMR confirmed that the compound is represented by the following formula (c-2). 【0048】 【0049】 [Synthesis Example 4] Synthesis of compound (C) A 2 L four-necked flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, and stirrer was prepared using the following formula (c-2) obtained in Synthesis Example 3 above. 100.0 g (0.196 mol) of the compound represented by , 30.5 g (0.216 mol) of 2-isocyanatoethyl acrylate, 0.1 g of 4-methoxyphenol, and 1000.0 g of tetrahydrofuran were mixed and heated and stirred at 50°C for 1 hour. Then, 1.0 g of tetrakis(2-ethylhexyl) orthotitanate was added and the mixture was heated and aged at 50°C for 6 hours. The solvent and unreacted substances were removed by vacuum distillation to obtain 117.5 g of the product. 【0050】 The resulting product is 1¹H-NMR confirmed that the compound is represented by the following formula (C). 【0051】 【0052】 [Synthesis Example 5] Synthesis of compound (D) A 1 L four-necked flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, and stirrer was prepared using the following formula (c-2) obtained in Synthesis Example 3 above. 27.0 g (5.30 × 10) of the compound represented by -2 480.0 g of tetrahydrofuran (ultra-dehydrated, stabilizer-free), 0.014 g of 4-methoxyphenol were added, and the mixture was heated and stirred at 35°C for 1 hour under a nitrogen atmosphere. Subsequently, 8.1 g of triethylamine (8.00 × 10) was added to the system. -2 After mixing 7.2 g (1.18 mol) of acrylate chloride with mol, the mixture was stirred at 35°C for 3 hours under a nitrogen atmosphere. Subsequently, the solvent, by-products, and unreacted materials were removed by methanol washing and reduced-pressure distillation to obtain 44.1 g of product. 【0053】 The resulting product is 1 ¹H-NMR confirmed that the compound is represented by the following formula (D). 【0054】 【0055】 [Synthesis Example 6] The synthesis of compound (E) was carried out in the same manner as in Synthesis Example 4, except that 100.0 g (0.196 mol) of compound (c-2) was replaced with 17.3 g (0.196 mol) of 3-pentanol, and 100.0 g of tetrahydrofuran (super-dehydrated, stabilizer-free) was used. 35.2 g of the product was obtained. 【0056】 The resulting product is 1 ¹H-NMR confirmed that the compound is represented by the following formula (E). 【0057】 【0058】 [Synthesis Example 7] The synthesis of compound (F) was carried out in the same manner as in Synthesis Example 4, except that 100.0 g (0.196 mol) of compound (c-2) was replaced with 53.0 g (0.196 mol) of 1-octadecanol, and 100.0 g of tetrahydrofuran (super-dehydrated, no stabilizer) was used. 68.7 g of the product was obtained. 【0059】 The obtained product was 1 confirmed by 1H-NMR to be a compound represented by the following formula (F). 【0060】 【0061】 [Example 1] In a 100 mL four-necked flask equipped with a thermometer, a nitrogen gas inlet, a reflux condenser, and a stirrer, 10.0 g (1.50×10 mol) of the monomer represented by the following formula (A) obtained in Synthesis Example 1 above, 23.3 g of tetrahydrofuran (ultra-dehydrated,不含 stabilizer) as a solvent, and 5.0 g of activated aluminum oxide were charged, and the mixture was stirred overnight at room temperature (25°C). After removing the aluminum oxide by pressure filtration, the mixture was distilled under reduced pressure at 50°C to remove 15.0 g of tetrahydrofuran and 0.087 g (5.30×10 -2 mol) of V-601 (dimethyl azobisisobutyrate, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a radical polymerization initiator were charged, and the reaction was carried out at 60°C for 20 hours under a nitrogen gas atmosphere. Then, 25 g of tetrahydrofuran was added for dilution, and the mixture was dropped into 500.0 g of methanol and reprecipitated as a solid. After obtaining the solid by pressure filtration, it was dried under reduced pressure while heating at 40°C. Then, tetrahydrofuran was added so that the active ingredient concentration became 3% by mass, and a coating solution of the polymer of the monomer represented by formula (A) was prepared. The weight average molecular weight of the obtained polymer of the monomer was 14,529. -4 【0062】 [Example 2] A coating solution with an active ingredient concentration of 3% by mass was prepared in the same manner as in Example 1, except that the monomer was changed from formula (A) to the monomer represented by the following formula (B), 40 g of tetrahydrofuran was added before the polymerization reaction, and no tetrahydrofuran was added before reprecipitation after the polymerization reaction. The weight average molecular weight of the obtained polymer of the monomer was 10,327. 【0063】 ​[Example 3] A coating solution with an active ingredient concentration of 3% by mass was prepared in the same manner as in Example 1, except that the monomer was changed from the monomer shown in formula (A) to the monomer shown in formula (C) below, and 0.016 parts by mass of V-601 was added as an initiator. The weight-average molecular weight of the polymer of the obtained monomer was 14,142. 【0064】 [Example 4] A coating solution with an active ingredient concentration of 3% by mass was prepared in the same manner as in Example 3, except that the monomer was changed from the monomer shown in formula (C) to the monomer shown in formula (D) below. The weight-average molecular weight of the polymer of the obtained monomer was 11,335. 【0065】 [Comparative Example 1] A coating solution with an active ingredient concentration of 3% by mass was prepared in the same manner as in Example 1, except that the monomer was changed from the monomer shown in formula (A) to the monomer shown in formula (E) below. The weight-average molecular weight of the polymer of the obtained monomer was 20,786. 【0066】 [Comparative Example 2] A coating solution with an active ingredient concentration of 3% by mass was prepared in the same manner as in Example 1, except that the monomer was changed from the monomer represented by formula (A) to the monomer represented by formula (F) below. The weight-average molecular weight of the polymer of the obtained monomer was 26,008. 【0067】 [Preparation of Glass Samples] The coating solutions prepared in Examples 1-4 and Comparative Examples 1-2 were dipped onto glass slides (S1127, 76 mm x 26 mm, manufactured by Matsunami Glass Industry Co., Ltd.) under the following conditions, and dried to prepare glass samples with a coating thickness of 0.10-0.20 μm. The thickness of the coating was measured using a spectroscopic ellipsometer (M-2000, manufactured by J.A. Wollam Co., Ltd.). <Dip Coating Conditions> Coating equipment: Tabletop dip coater (DT-0303-S3, manufactured by SDI Co., Ltd.) Immersion time: 30 seconds Withdrawal speed: 3 mm / sec Drying after coating: Room temperature (25°C), 30 minutes 【0068】[Water Contact Angle, Hexadecane (HD) Contact Angle] For the glass samples prepared as described above, the contact angles (water repellency and oil repellency) of the coated film with respect to water and hexadecane (HD) were measured using a Drop Master contact angle meter (Kyowa Interface Science Co., Ltd., DMo-701SA) (droplet: 2 μL, temperature: 25°C, relative humidity: 40%). The measurement was performed by photographing the pure water and hexadecane 1 second after dropping with a CCD camera connected to the contact angle meter, and measuring the contact angle between the glass substrate and the droplet. The droplet image was analyzed using FAMAS contact angle analysis software attached to the above contact angle measuring instrument, and the contact angle between the glass substrate and the droplet was measured. The contact angle was calculated using the θ / 2 method. The analysis conditions are as follows. The results (water contact angle and HD contact angle) are shown in Table 1. Initially, the example showed good water repellency and oil repellency. [Analysis Conditions] Method: Droplet method (θ / 2 method) Droplet recognition: Automatic Droplet recognition line (distance from needle tip): 50 dots Algorithm: Automatic Image mode: Frame Threshold level: Automatic [Evaluation Criteria] Pure water contact angle ○: 105° or more △: 100° or more, less than 105° ×: Less than 100° HD contact angle ○: 40° or more △: 35° or more, less than 40° ×: Less than 35° 【0069】

Claims

1. A non-fluorine surface treatment agent for imparting water-repellent and oil-repellent properties to a substrate surface, comprising a polymer in which an acrylate monomer is a monomer component, wherein an acryloyl group or an α-substituted acryloyl group and two or three monovalent aliphatic hydrocarbon groups having 10 to 40 carbon atoms are bonded via a trivalent or tetravalent linking group, and the two or three monovalent aliphatic hydrocarbon groups having 10 to 40 carbon atoms are bonded to the same atom in the trivalent or tetravalent linking group.

2. The surface treatment agent according to claim 1, wherein the two or three monovalent aliphatic hydrocarbon groups are the same.

3. The above acrylate monomer is of the following general formula (I) The surface treatment agent according to claim 1, wherein the monomer is represented by the formula: [wherein X is a hydrogen atom, a halogen atom, an alkyl group or an aryl group; Y is a single bond, or a divalent hydrocarbon group having 1 to 10 carbon atoms that may contain one or more selected from the group consisting of an oxygen atom, -NR'- (where R' is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), an amide bond, a urethane bond and a urea bond; Z is a carbon atom, nitrogen atom or silicon atom to which R is bonded, or a trivalent or tetravalent linking group containing said carbon atom, nitrogen atom or silicon atom; R is a monovalent hydrocarbon group having 10 to 40 carbon atoms; and n is 2 or 3. All Rs are bonded to the same carbon atom, nitrogen atom or silicon atom in Z.] 4. The surface treatment agent according to claim 3, wherein X in general formula (I) is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, or a phenyl group.

5. The surface treatment agent according to claim 3, wherein the trivalent or tetravalent linking group Z in the general formula (I) is a carbon atom, a nitrogen atom, a silyl group, a silyl ether group, or a group represented by the following formula (1).

6. The surface treatment agent according to claim 5, wherein the trivalent or tetravalent linking group of Z in general formula (I) is a carbon atom, a nitrogen atom, or a group represented by the following formula (1).

7. The surface treatment agent according to claim 1, which provides a coating on a glass plate having a water contact angle of 100° or more when applied to the glass plate.

8. The surface treatment agent according to claim 1, which provides a coating on a glass plate having a hexadecane contact angle of 35° or more when applied to the glass plate.

9. An article having a coating film of the surface treatment agent described in claims 1 to 8 on its surface.

Images