Amide group-containing silicon compound and water and oil repellency-imparting agent

Abstract

To provide an amide group-containing silicon compound excellent in slip-down property of droplets from a substrate surface.SOLUTION: The amide group-containing silicon compound is a reaction product of an amide group-containing monomer (A) represented by formula (1) and an organosilicon compound (B) represented by formula (2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an amide group-containing silicon compound and a water- and oil-repellent agent containing the amide group-containing silicon compound. [Background technology]

[0002] Silane coupling agents, a type of organosilicon compound, can combine the reactivity of alkoxysilane moieties with the functionality of various functional groups, and a variety of compounds have been reported. Among these, silane coupling agents containing fluorine alkyl groups can impart both water and oil repellency to the surface of substrates such as glass. They are characterized by the fact that water and oil droplets adhering to the substrate surface immediately slide off and are removed, making it difficult for minute impurities contained in the droplets to remain on the substrate surface. Therefore, with the aim of preventing contamination of substrate surfaces by a wide range of water-based and oil-based substances, they are used as water- and oil-repellent agents for various substrates in a wide range of fields, including electronic materials and automotive materials (Patent Document 1).

[0003] On the other hand, regulations on various fluorine-containing compounds are currently being strengthened from the viewpoint of their residual properties in the environment, and fluorine-based silane coupling agents contained in water and oil repellency imparting agents are also listed as targets. Therefore, there is a demand for alternatives to fluorine-based silane coupling agents, and a silane coupling agent that is non-fluorine-based and has excellent water repellency has been proposed (Patent Document 2). However, conventional non-fluorine-based silane coupling agents have difficulty achieving both water and oil repellency, and liquid droplets adhering to the substrate surface do not slide off easily, so their applications as water and oil repellency imparting agents have been limited. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-196644 [Patent Document 2] Japanese Patent Application Publication No. 2019-73495 Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is to provide an amide group-containing silicon compound and a water- and oil-repellent agent containing an amide group-containing silicon compound that can provide water- and oil-repellent properties equivalent to those of conventional water- and oil-repellent agents containing fluorine-based silane coupling agents and that are excellent in the ability to allow liquid droplets to slide off the surface of a substrate. [Means for solving the problem]

[0006] As a result of intensive research in light of the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using an amide group-containing silicon compound obtained by reacting a specific amide group-containing monomer with an organosilicon compound having a specific functional group. That is, the present invention relates to the following [1] to [2].

[0007] [1] An amide group-containing silicon compound which is a reaction product of an amide group-containing monomer (A) represented by the following formula (1) and an organosilicon compound (B) represented by the following formula (2): [ka] [In formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is a hydrocarbon group having 1 to 23 carbon atoms, and R 4 is a hydrogen atom or a methyl group. [ka] [In formula (2), R 5 ~R 7 each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and R 5 ~R 7at least one of R is an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms; 8 and R 9 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms, X is -NH2 or -SH, and a is 0 or 1.] [2] A water- and oil-repellent agent comprising the amide group-containing silicon compound described in [1] above. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide an amide group-containing silicon compound and a water- and oil-repellent agent containing an amide group-containing silicon compound that can exhibit water- and oil-repellency equivalent to that of conventional water- and oil-repellent agents containing fluorine-based silane coupling agents and that are excellent in the ability to allow liquid droplets to slide off the surface of a substrate. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is an LC-MS chart of the amide group-containing silicon compound obtained in Synthesis Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited to the embodiment described in this specification and can be modified in various ways without departing from the gist of the present invention. In this specification, numerical ranges defined using the symbol "to" are inclusive of the numerical values ​​at both ends (upper and lower limits) of the symbol "to." For example, "2 to 5" means 2 or more and 5 or less. The amide group-containing silicon compound of the present invention is a reaction product of the amide group-containing monomer represented by the above formula (1) and the organosilicon compound represented by formula (2), and can be obtained by reacting the amide group-containing monomer with the organosilicon compound. The details of each component and the amide group-containing silicon compound of the present invention, as well as the production method and usage method thereof, will be explained below.

[0011] <Amide group-containing monomer represented by formula (1)> The amide group-containing monomer according to the present invention is represented by the following formula (1). [ka] In formula (1), R 1 is a hydrogen atom or a methyl group. 1 is more preferably a hydrogen atom from the viewpoint of water and oil repellency. R 2 is a hydrocarbon group having 1 to 6 carbon atoms. 2 R may be a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, a saturated hydrocarbon group, or an unsaturated hydrocarbon group. 2 The number of carbon atoms in R is more preferably 1 to 4, and even more preferably 2. 2 is particularly preferably an alkylene group, and from the viewpoint of availability, a methylene group, an ethylene group, a trimethylene group, or a tetramethylene group is more preferred, and an ethylene group is even more preferred.

[0012] R 3 is a hydrocarbon group having 1 to 23 carbon atoms. 3 R may be a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, a saturated hydrocarbon group, or an unsaturated hydrocarbon group. 3 The number of carbon atoms in R is preferably 12 to 21, and particularly preferably 15 to 21. 3 Although the alkyl group may be a straight-chain alkyl group or a branched alkyl group, a straight-chain alkyl group having 1 to 21 carbon atoms, which is easily available, is particularly preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a heptyl group, a dodecyl group, a tetradecyl group, a pentadecyl group, a heptadecyl group, a nonadecyl group, and an eicosyl group. R 4 is a hydrogen atom or a methyl group, and is more preferably a hydrogen atom. The amide group-containing monomer represented by formula (1) may be used alone or in combination of two or more kinds.

[0013] Specific examples of amide group-containing monomers include acetic acid amidoethyl (meth)acrylate, propionic acid amidoethyl (meth)acrylate, butyric acid amidoethyl (meth)acrylate, valeric acid amidoethyl (meth)acrylate, caproic acid amidoethyl (meth)acrylate, caprylic acid amidoethyl (meth)acrylate, 2-ethylhexanoic acid amidoethyl (meth)acrylate, capric acid amidoethyl (meth)acrylate, lauric acid amidoethyl (meth)acrylate, myristate acid amidoethyl (meth)acrylate, palmitate acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, and arachidic acid amidoethyl (meth)acrylate. acrylate, behenic acid amidoethyl (meth)acrylate, isostearic acid amidoethyl (meth)acrylate, oleic acid amidoethyl (meth)acrylate, myristoleic acid amidoethyl (meth)acrylate, palmitoleic acid amidoethyl (meth)acrylate, petroselinic acid amidoethyl (meth)acrylate, acetic acid amidopropyl (meth)acrylate, 2-ethylhexanoic acid amidopropyl (meth)acrylate, lauric acid amidopropyl (meth)acrylate, palmitic acid amidopropyl (meth)acrylate, stearic acid amidopropyl (meth)acrylate, behenic acid amidopropyl (meth)acrylate, or mixtures thereof.

[0014] The amide group-containing monomer is preferably selected from acetic acid amidoethyl (meth)acrylate, 2-ethylhexanoic acid amidoethyl (meth)acrylate, lauric acid amidoethyl (meth)acrylate, palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, and behenic acid amidoethyl (meth)acrylate, and more preferably selected from palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate, and behenic acid amidoethyl (meth)acrylate. In the present invention, the amide group-containing monomers may be used alone or in combination of two or more.

[0015] The method for producing the amide group-containing monomer represented by formula (1) is not particularly limited, but it can be produced, for example, by the following methods (1) to (3). (1) In the presence of an acid catalyst, (meth)acrylic acid and an alkanolamide are subjected to a dehydration esterification reaction to produce an amide group-containing monomer represented by formula (1). (2) In the presence of a transesterification catalyst, a (meth)acrylic acid ester and an alkanolamide are subjected to a transesterification reaction to produce an amide group-containing monomer represented by formula (1). (3) (Meth)acrylic acid chloride is reacted with an alkanolamide to produce an amide group-containing monomer represented by formula (1).

[0016] <Organosilicon compound represented by formula (2)> The organosilicon compound according to the present invention is represented by the following formula (2). [ka] [In formula (2), R 5 ~R 7 each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and R 5 ~R 7 at least one of R is an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms; 8 and R 9 each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms, X is -NH2 or -SH, and a is 0 or 1.]

[0017] In equation (2), R 5 ~R 7 are each independently preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 2 carbon atoms, and among these, R 5 ~R 7 It is more preferable that each of R is an alkoxy group having one carbon atom (a methoxy group). 8is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and even more preferably an alkylene group having 2 to 4 carbon atoms. 9 is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms. X is -NH2 or -SH. a is 0 or 1, and is more preferably 0.

[0018] The organosilicon compound represented by formula (2) can be selected from compounds containing an amino group or a mercapto group. Among the organosilicon compounds represented by formula (2), examples of compounds containing an amino group include N-2-(aminoethyl)-aminomethyltrimethoxysilane, N-2-(aminoethyl)-aminomethyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, N-2-(aminoethyl)-8-aminooctyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, Examples of the silane include 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 8-aminooctyltrimethoxysilane, and 8-aminooctyltriethoxysilane. From the viewpoint of reactivity, however, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and N-2-(aminoethyl)-3-aminopropyltriethoxysilane are preferred, 3-aminopropyltrimethoxysilane and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane are more preferred, and 3-aminopropyltrimethoxysilane is even more preferred.

[0019] Furthermore, among the organosilicon compounds represented by formula (2), examples of compounds containing a mercapto group include mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptoisobutyltrimethoxysilane, 3-mercapto-2-hydroxypropyltrimethoxysilane, 3-mercapto-2-hydroxypropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane. From the viewpoint of reactivity, however, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane are preferred. In the present invention, any one of the organosilicon compounds may be used alone, or two or more of them may be used in combination.

[0020] <Amido group-containing silicon compounds> The amide group-containing silicon compound of the present invention is a compound obtained by forming a covalent bond through a Michael addition reaction between the (meth)acryloyl group of the amide group-containing monomer represented by the above formula (1) and the amino group or mercapto group of the organosilicon compound represented by formula (2). That is, the amide group-containing silicon compound of the present invention is a Michael addition reaction product of the amide group-containing monomer (A) represented by formula (1) and the organosilicon compound (B) represented by formula (2). The Michael addition reaction can be carried out at room temperature with or without a catalyst, but the reaction rate can be increased by using a catalyst. Examples of catalysts include metal alkoxides, piperidine, quaternary ammonium salts, and tertiary phosphines. Among these, tertiary phosphines are preferred due to their high catalytic activity and ease of handling, and triphenylphosphine is even more preferred.

[0021] The Michael addition reaction can be carried out in a solvent, and examples of suitable solvents include monool solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, isobutyl alcohol, pentanol, methylbutanol, neopentyl alcohol, isopentyl alcohol, 1-hexanol, 2-hexanol, 1-heptanol, 2-heptanol, 1-octanol, 2-octanol, cyclohexanol, and methylcyclohexanol; methoxyethanol, ethoxyethanol, methoxymethoxyethanol, isopropoxyethanol, butoxyethanol, isopentyloxyethanol, hexyloxyethanol, phenoxyethanol, benzyloxyethanol, diethylene glycol, and diethylene glycol monomethyl ether. Examples of suitable solvents include ether alcohol solvents such as ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, polyethylene glycol, methoxypropanol (propylene glycol monomethyl ether), ethoxypropanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and polypropylene glycol; hydroxypropionitrile; and amino alcohol solvents such as aminoethanol, dimethylaminoethanol, diethylaminoethanol, diethanolamine, N-butyldiethanolamine, and triethanolamine.

[0022] In addition to the above, the following ether solvents, ketone solvents, hydrocarbon solvents, ester solvents, etc. may also be used as the solvent for the Michael addition reaction.

[0023] Examples of ether solvents include aliphatic hydrocarbon ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, and dibutyl ether; aromatic hydrocarbon ether solvents such as butyl phenyl ether, pentyl phenyl ether, methoxytoluene, benzyl ethyl ether, diphenyl ether, and dibenzyl ether; cyclic ether solvents such as propylene oxide, furan, and tetrahydrofuran; and polyether solvents such as 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and glycerin ether.

[0024] Examples of ketone solvents include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and acetophenone. Examples of hydrocarbon solvents include saturated aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, and decane; aromatic hydrocarbon solvents such as toluene and xylene; and saturated alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.

[0025] Ester solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl Examples of the solvent include acetate solvents such as ether acetate, propylene glycol monomethyl ether acetate, methyl acetoacetate, and ethyl acetoacetate; propionate solvents such as methyl propionate, ethyl propionate, butyl propionate, and isopentyl propionate; γ-butyrolactone; ethylene glycol monoacetate; ethylene diacetate; ethylene glycol esters; diethylene glycol monoacetate; carbonate esters such as diethyl carbonate, ethylene carbonate, and propylene carbonate; and lactate esters such as ethyl lactate. These solvents may be used alone or in combination of two or more.

[0026] <Water and oil repellency imparting agent> The present invention can provide a water- and oil-repellency imparting agent containing the above-mentioned amide group-containing silicon compound. The content of the amide group-containing silicon compound of the present invention in the water- and oil-repellency imparting agent of the present invention is preferably 0.001 to 30 mass %, more preferably 0.01 to 10 mass %, and even more preferably 0.1 to 1 mass %, calculated as the active ingredient, based on the total mass of the water- and oil-repellency imparting agent.

[0027] The form of the water- and oil-repellent agent of the present invention is not particularly limited and may be, for example, a solution, emulsion, paste, or spray. The water- and oil-repellent agent of the present invention may also be used in the form of being impregnated into or coated on a sheet such as a sponge or nonwoven fabric. The water- and oil-repellent agent of the present invention can be applied to the target substrate by known methods such as brushing, dipping, or spraying. The water- and oil-repellency imparting agent of the present invention can be applied to any substrate, including various materials such as paper, cloth, metals and their oxides, leather, synthetic leather, resin, wood, glass, resin films, ceramics, quartz, and stone, as well as the surfaces of coating films formed on these substrates with various paints. The water- and oil-repellent agent of the present invention may contain other components different from the amide group-containing silicon compound of the present invention, as needed, as long as the effects of the present invention are not impaired. Examples of such other components include, but are not limited to, powder components such as metal powder and glass powder, liquid oils and fats, solid oils and fats, hydrocarbons, higher fatty acids, higher alcohols, lower alcohols, polyhydric alcohols, esters, silicones, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, water-soluble polymers, thickeners, UV absorbers, sequestering agents, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, antioxidants, antioxidant aids, chelating agents, acid catalysts, base catalysts, crosslinkers, antibacterial agents, lubricants, neutralizing agents, pigments, dyes, glidants, leveling agents, dispersants, viscosity modifiers, foaming agents, defoamers, preservatives, preservative aids, fragrances, water, and solvents. These other components may be used alone or in combination. [Example]

[0028] The following examples and comparative examples will be used to explain the embodiments of the present invention in more detail, but the present invention is not limited to these examples. In each synthesis example, the compounds obtained were identified using LC-MS (column: Cadenza CD-C18 (Imtakt, length 100 mm, inner diameter φ3 mm, particle size 3 μm), column temperature: 40°C, ionization mode: ESI+, mobile phase: 5 mM CH3COONH4 methanol solution / IPA=70 / 30).

[0029] The amide group-containing monomers and organosilicon compounds used in the following synthesis examples are shown in Table 1 below. [Table 1]

[0030] <Synthesis Example 1> A 1 L four-neck flask equipped with a thermometer, stirrer, and Dimroth condenser was charged with 50 g of palmitic acid amidoethyl acrylate (A4), 20 g of 3-aminopropyltrimethoxysilane (B1), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50 °C. After the internal temperature of the reaction solution reached 50 °C, it was stirred for 6 hours and then cooled to room temperature, yielding a pale yellow solution. The resulting solution was analyzed by LC-MS, confirming that it contained an amide group-containing silicon compound (molecular weight 533), the reaction product of palmitic acid amidoethyl acrylate (A4) and 3-aminopropyltrimethoxysilane (B1).

[0031] <Synthesis Example 2> A 1 L four-neck flask equipped with a thermometer, stirrer, and Dimroth condenser was charged with 50 g of palmitic acid amidoethyl acrylate (A4), 20 g of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (B2), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50 °C. After the internal temperature of the reaction solution reached 50 °C, it was stirred for 6 hours and then cooled to room temperature to obtain a pale yellow solution. The resulting solution was analyzed by LC-MS and confirmed to contain an amide group-containing silicon compound (molecular weight 576), which is the reaction product of palmitic acid amidoethyl acrylate (A4) and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (B2).

[0032] <Synthesis Example 3> A 1 L four-neck flask equipped with a thermometer, stirrer, and Dimroth condenser was charged with 50 g of palmitic acid amidoethyl acrylate (A4), 20 g of N-2-(aminoethyl)-8-aminooctyltrimethoxysilane (B3), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50 °C. After the internal temperature of the reaction solution reached 50 °C, it was stirred for 6 hours and then cooled to room temperature to obtain a pale yellow solution. The resulting solution was analyzed by LC-MS and confirmed to contain an amide group-containing silicon compound (molecular weight 646), which was the reaction product of palmitic acid amidoethyl acrylate (A4) and N-2-(aminoethyl)-8-aminooctyltrimethoxysilane (B3).

[0033] <Synthesis Example 4> A 1 L four-neck flask equipped with a thermometer, stirrer, and Dimroth condenser was charged with 50 g of palmitic acid amidoethyl acrylate (A4), 20 g of 3-aminopropyltriethoxysilane (B4), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50 °C. After the internal temperature of the reaction solution reached 50 °C, it was stirred for 6 hours and then cooled to room temperature, yielding a pale yellow solution. The resulting solution was analyzed by LC-MS and confirmed to contain an amide group-containing silicon compound (molecular weight 575), the reaction product of palmitic acid amidoethyl acrylate (A4) and 3-aminopropyltriethoxysilane (B4).

[0034] <Synthesis Example 5> A 1 L four-neck flask equipped with a thermometer, stirrer, and Dimroth condenser was charged with 50 g of palmitic acid amidoethyl acrylate (A4), 20 g of 3-mercaptopropyltrimethoxysilane (B5), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50 °C. After the internal temperature of the reaction solution reached 50 °C, it was stirred for 6 hours and then cooled to room temperature, yielding a pale yellow solution. The resulting solution was analyzed by LC-MS and confirmed to contain an amide group-containing silicon compound (molecular weight 550), which was the reaction product of palmitic acid amidoethyl acrylate (A4) and 3-mercaptopropyltrimethoxysilane (B5).

[0035] <Synthesis Example 6> A 1 L four-neck flask equipped with a thermometer, stirrer, and Dimroth condenser was charged with 50 g of acetic acid amide ethyl acrylate (A1), 20 g of 3-aminopropyltrimethoxysilane (B1), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50 °C. After the internal temperature of the reaction solution reached 50 °C, it was stirred for 6 hours and then cooled to room temperature, yielding a pale yellow solution. The resulting solution was analyzed by LC-MS, confirming that it contained an amide group-containing silicon compound (molecular weight 336), which was the reaction product of acetic acid amide ethyl acrylate (A1) and 3-aminopropyltrimethoxysilane (B1).

[0036] <Synthesis Example 7> A 1 L four-neck flask equipped with a thermometer, stirrer, and Dimroth condenser was charged with 50 g of 2-ethylhexanoic acid amidoethyl acrylate (A2), 20 g of 3-aminopropyltrimethoxysilane (B1), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50 °C. After the internal temperature of the reaction solution reached 50 °C, it was stirred for 6 hours and then cooled to room temperature to obtain a pale yellow solution. The resulting solution was analyzed by LC-MS and confirmed to contain an amide group-containing silicon compound (molecular weight 421), which was the reaction product of 2-ethylhexanoic acid amidoethyl acrylate (A2) and 3-aminopropyltrimethoxysilane (B1).

[0037] <Synthesis Example 8> A 1 L four-neck flask equipped with a thermometer, stirrer, and Dimroth condenser was charged with 50 g of lauric acid amide ethyl acrylate (A3), 20 g of 3-aminopropyltrimethoxysilane (B1), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50 °C. After the internal temperature of the reaction solution reached 50 °C, the mixture was stirred for 6 hours and then cooled to room temperature, yielding a pale yellow solution. The resulting solution was analyzed by LC-MS, confirming that it contained an amide group-containing silicon compound (molecular weight 477), which was the reaction product of lauric acid amide ethyl acrylate (A3) and 3-aminopropyltrimethoxysilane (B1).

[0038] <Synthesis Example 9> A 1 L four-neck flask equipped with a thermometer, stirrer, and Dimroth condenser was charged with 50 g of behenamidoethyl acrylate (A5), 20 g of 3-aminopropyltrimethoxysilane (B1), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50 °C. After the internal temperature of the reaction solution reached 50 °C, it was stirred for 6 hours and then cooled to room temperature, yielding a pale yellow solution. The resulting solution was analyzed by LC-MS, confirming that it contained an amide group-containing silicon compound (molecular weight 617), the reaction product of behenamidoethyl acrylate (A5) and 3-aminopropyltrimethoxysilane (B1).

[0039] <Synthesis Example 10> A 1 L four-neck flask equipped with a thermometer, stirrer, and Dimroth condenser was charged with 50 g of palmitic acid amidoethyl methacrylate (A6), 20 g of 3-aminopropyltrimethoxysilane (B1), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50 °C. After the internal temperature of the reaction solution reached 50 °C, it was stirred for 6 hours and then cooled to room temperature, yielding a pale yellow solution. The resulting solution was analyzed by LC-MS and confirmed to contain an amide group-containing silicon compound (molecular weight 547), the reaction product of palmitic acid amidoethyl methacrylate (A6) and 3-aminopropyltrimethoxysilane (B1).

[0040] <Synthesis Example 11> A 1 L four-neck flask equipped with a thermometer, a stirrer, and a Dimroth condenser was charged with 50 g of palmitic acid amide ethyl acrylate (A4), 100 g of cyclohexane, and 100 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50°C. After the internal temperature of the solution reached 50°C, the mixture was stirred for 6 hours and then cooled to room temperature, yielding a pale yellow solution containing an amide group-containing monomer.

[0041] <Synthesis Example 12> A 1 L four-neck flask equipped with a thermometer, a stirrer, and a Dimroth condenser was charged with 20 g of 3-aminopropyltrimethoxysilane (B1), 40 g of cyclohexane, and 40 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50°C. After the internal temperature of the solution reached 50°C, the mixture was stirred for 6 hours and then cooled to room temperature, yielding a solution containing an organosilane compound.

[0042] <Synthesis Example 13> A 1 L four-neck flask equipped with a thermometer, a stirrer, and a Dimroth condenser was charged with 20 g of decyltrimethoxysilane (B'1), 40 g of cyclohexane, and 40 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50°C. After the internal temperature of the reaction solution reached 50°C, the mixture was stirred for 6 hours and then cooled to room temperature, yielding a solution containing an organosilane compound.

[0043] <Synthesis Example 14> A 1 L four-neck flask equipped with a thermometer, a stirrer, and a Dimroth condenser was charged with 50 g of palmitic acid amidoethyl acrylate (A4), 20 g of decyltrimethoxysilane (B'1), 140 g of cyclohexane, and 140 g of 2-propanol, and the mixture was heated in a water bath until the internal temperature reached 50°C. After the internal temperature of the reaction solution reached 50°C, the mixture was stirred for 6 hours and then cooled to room temperature, yielding a solution containing an amide group-containing monomer and an organosilane compound. The raw materials and amounts used in each of the above synthesis examples are shown in Table 2.

[0044] Example 1 0.1 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 1 and 99.9 g of 2-propanol were placed in a glass container and stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0045] <Example 2> 0.5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 1 and 99.5 g of 2-propanol were placed in a glass container and stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0046] Example 3 5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 1 and 95 g of 2-propanol were placed in a glass container and stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0047] Example 4 50 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 1 and 50 g of 2-propanol were placed in a glass container and stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0048] <Example 5> 0.5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 2 and 99.5 g of 2-propanol were placed in a glass container and stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0049] Example 6 0.5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 3 and 99.5 g of 2-propanol were placed in a glass vessel and stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0050] Example 7 0.5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 4 and 99.5 g of 2-propanol were placed in a glass container and stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0051] Example 8 A glass vessel was charged with 0.5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 5 and 99.5 g of 2-propanol, and the mixture was stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0052] Example 9 In a glass vessel, 0.5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 6 and 99.5 g of 2-propanol were placed and stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0053] Example 10 In a glass vessel, 0.5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 7 and 99.5 g of 2-propanol were placed and stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0054] Example 11 A glass vessel was charged with 0.5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 8 and 99.5 g of 2-propanol, and the mixture was stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0055] Example 12 In a glass vessel, 0.5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 9 and 99.5 g of 2-propanol were placed and stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0056] Example 13 A glass vessel was charged with 0.5 g of the solution of the amide group-containing silicon compound obtained in Synthesis Example 10 and 99.5 g of 2-propanol, and the mixture was stirred at room temperature for 1 hour to obtain a water- and oil-repellent agent.

[0057] <Comparative Example 1> A glass container was charged with 0.5 g of the solution of the amide group-containing monomer obtained in Synthesis Example 11 and 99.5 g of 2-propanol, and the mixture was stirred at room temperature for 1 hour to obtain a surface modifier.

[0058] <Comparative Example 2> A glass container was charged with 0.5 g of the solution of the organosilane compound obtained in Synthesis Example 12 and 99.5 g of 2-propanol, and the mixture was stirred at room temperature for 1 hour to obtain a surface modifier.

[0059] <Comparative Example 3> A glass container was charged with 0.5 g of the solution of the organosilane compound obtained in Synthesis Example 13 and 99.5 g of 2-propanol, and the mixture was stirred at room temperature for 1 hour to obtain a surface modifier.

[0060] <Comparative Example 4> A glass container was charged with 0.5 g of the solution of the mixture of the amide group-containing monomer and the organosilane compound obtained in Synthesis Example 14 and 99.5 g of 2-propanol, and the mixture was stirred at room temperature for 1 hour to obtain a surface modifier.

[0061] The water- and oil-repellency imparting agents obtained in the examples and the surface modifiers obtained in the comparative examples were evaluated as follows, and the results are shown in Tables 3 and 4.

[0062] <Evaluation of water repellency (contact angle)> The water- and oil-repellent agents of Examples 1 to 13 and the surface modifiers of Comparative Examples 1 to 4 were applied to glass substrates and heated on a hot plate at 120°C for 1 minute to obtain evaluation substrates. Using these surface-modified evaluation substrates, the contact angle of ion-exchanged water with the substrate surface was measured using an automatic contact angle meter, DropMaster R501Hi (manufactured by Kyowa Interface Science Co., Ltd.). In this evaluation, a larger contact angle indicates better water repellency. The evaluation criteria are as follows: ◎: The contact angle is 100° or more. ○: The contact angle is 70° or more and less than 100°. ×: The contact angle is less than 70°.

[0063] <Evaluation of water droplet removal (slide angle)> The water- and oil-repellent agents of Examples 1 to 13 and the surface modifiers of Comparative Examples 1 to 4 were applied to glass substrates and heated on a hot plate at 120°C for 1 minute to obtain evaluation substrates. Using these surface-modified evaluation substrates, the ability to remove water droplets from the substrate surface was evaluated by measuring the angle at which a water droplet begins to slide (sliding angle) when the substrate surface is gradually tilted using an automatic contact angle meter, DropMaster R501Hi (manufactured by Kyowa Interface Science Co., Ltd.). In this evaluation, a smaller sliding angle indicates better water droplet removal ability. The evaluation criteria are as follows: ◎: The sliding angle is less than 30°. ○: The sliding angle is 30° or more and less than 60°. ×: The sliding angle is 60° or more.

[0064] <Oil repellency evaluation (contact angle)> The water- and oil-repellent agents of Examples 1 to 13 and the surface modifiers of Comparative Examples 1 to 4 were applied to glass substrates and heated on a hot plate at 120°C for 1 minute to obtain evaluation substrates. Using these surface-modified evaluation substrates, the contact angle of hexadecane with the substrate surface was measured using an automatic contact angle meter, DropMaster R501Hi (manufactured by Kyowa Interface Science Co., Ltd.). In this evaluation, a larger contact angle indicates better oil repellency. The evaluation criteria are as follows: ◎: The contact angle is 40° or more. ○: The contact angle is 20° or more and less than 40°. ×: The contact angle is less than 20°.

[0065] [Table 2]

[0066] [Table 3]

[0067] [Table 4]

[0068] Examples 1 to 13 according to the present invention were excellent in all physical properties. In contrast, Comparative Example 1 did not contain the organosilicon compound (B) and had insufficient water droplet removal properties. Comparative Example 2 did not contain the amide group-containing monomer (A) and had insufficient water repellency, water droplet removal properties, and oil repellency. Comparative Example 3 contained an organosilicon compound different from the organosilicon compound (B) and had insufficient oil repellency. Comparative Example 4 contained an organosilicon compound different from the amide group-containing monomer (A) and organosilicon compound (B) and had insufficient oil repellency.

Claims

1. An amide group-containing silicon compound which is a reaction product of an amide group-containing monomer (A) represented by the following formula (1) and an organosilicon compound (B) represented by the following formula (2). 【Chemistry 1】 [In formula (1), R １ is a hydrogen atom or a methyl group, and R ２ is a hydrocarbon group having 1 to 6 carbon atoms, and R ３ is a hydrocarbon group having 1 to 23 carbon atoms, and R ４ is a hydrogen atom or a methyl group. 【Chemistry 2】 [In formula (2), R ５ ~R ７ each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group; R ５ ~R ７ at least one of R is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group; ８ and R ９ each independently represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and X represents -NH ２ or —SH, and a is 0 or 1.]

2. A water- and oil-repellent agent comprising the amide group-containing silicon compound according to claim 1.

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