Oil-repellent surface treatment composition

Abstract

The object of this invention is to provide a surface treatment composition that has low environmental concerns and excellent oil repellency. [Solution] An oil-repellent surface treatment composition comprising a compound represented by formula (1) and / or a compound represented by formula (2) as a solute component. TIFF2026046280000034.tif20123TIFF2026046280000035.tif24129

Description

[Technical Field]

[0001] This invention relates to an oil-repellent surface treatment composition. [Background technology]

[0002] Conventionally, compositions containing a fluorine-containing polymer and a solvent are known as waterproof and moisture-proof coating agents. It is also known that the fluorine-containing polymer may contain structural units formed by (meth)acrylic acid esters having phenyl groups (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 6670615 [Overview of the project] [Problems that the invention aims to solve]

[0004] Compounds containing perfluoroalkyl groups are known to generate perfluorocarboxylic acids and other compounds during their decomposition process. Among perfluorocarboxylic acids, PFOS (perfluorooctanesulfonic acid) and PFOA (perfluorooctanoic acid) are known to have high chemical stability, but are also difficult to decompose in the environment and have high bioaccumulation potential. As a result, various scientific discussions are taking place internationally regarding their target values ​​and standards, and they are becoming regulated substances in many countries. On the other hand, PFHxA (perfluorohexanoic acid) and perfluorocarboxylic acids with even shorter carbon chains have been confirmed to have far lower biotoxicity and bioaccumulation compared to PFOS and PFOA. Therefore, perfluoroalkyl group-containing compounds whose degradation products are PFHxA or perfluorocarboxylic acids with even shorter carbon chains are widely used as alternative technologies. However, even with these alternative compounds, the perfluorocarboxylic acid, which is a decomposition product, remains chemically stable. Therefore, concerns remain that if these compounds continue to be released into the environment, they will accumulate over many years and affect human health and the environment. For this reason, there is a demand for new alternative compounds. On the other hand, compounds containing a trifluoromethoxy group are known to decompose easily in the environment (for example, at temperatures above -20°C) because CF3OH, which is expected to be generated during the decomposition process, is a very unstable compound.

[0005] Therefore, the object of the present invention is to provide a surface treatment composition that has low environmental concerns and excellent oil repellency. [Means for solving the problem]

[0006] As a result of diligent research to solve the above problems, the inventors have found that the problems can be solved by the following configuration.

[0007] [1] An oil-repellent surface treatment composition comprising a compound represented by formula (1) and / or a compound represented by formula (2) as a solute component. [ka] In formula (1), Each X independently represents either O or a single bond. Q1 independently represents a single bond or a divalent organic group. Q2 represents a single bond or a (p+q) valence linking group. Y independently represents either -COOH or -SO3H. p and q each independently represent numbers from 1 to 3. m represents 1 through 5. [ka] In formula (2), Each X independently represents either O or a single bond. Q1 independently represents a single bond or a divalent organic group. Q2 each independently represents a single bond or a (p + 1)-valent linking group, n represents 1 to 2, p represents 1 to 3, m represents 1 to 5. [2] The oil-repellent surface treatment composition according to [1], further containing a base. [3] The oil-repellent surface treatment composition according to [1] or [2], wherein X in formula (1) and / or X in formula (2) is O. [4] The oil-repellent surface treatment composition according to any one of [1] to [3], wherein Q1 in formula (1) and / or Q1 in formula (2) is a single bond. [5] The oil-repellent surface treatment composition according to any one of [1] to [4], containing a solvent, and the solvent is non-flammable. [6] The oil-repellent surface treatment composition according to any one of [1] to [4], containing an aqueous solvent, and the main component of the aqueous solvent is water. [Effect of the Invention]

[0008] According to the present invention, it is possible to provide a surface treatment composition with low environmental concerns and excellent oil repellency. [Brief Description of the Drawings]

[0009] [Figure 1] Figure 1 is a 1H-NMR chart of the compound finally produced in Preparation Example 1. [Figure 2] Figure 2 is a 19F-NMR chart of the compound finally produced in Preparation Example 1. [Figure 3] Figure 3 is a 31P-NMR chart of the compound finally produced in Preparation Example 1. [Mode for Carrying Out the Invention]

[0010] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, each component may be used individually or in combination of two or more. In this specification, when two or more ingredients are used in combination, the "content" of those ingredients means the total content of those two or more ingredients unless otherwise specified. In this specification, the method for producing each component is not particularly limited unless otherwise specified. For example, conventionally known methods may be used. In this specification, commercially available products may be used as each component. In this specification, the oil-repellent surface treatment composition of the present invention is also referred to as the surface treatment composition of the present invention, or the composition of the present invention. In this specification, the lower environmental concern and / or superior oil repellency of the surface treatment composition of the present invention is also referred to as "superior effects of the present invention." In this specification, a compound represented by formula (*) may be simply referred to as "formula (*)". For example, a compound represented by formula (1) may be simply referred to as "formula (1)". In this specification, the collective concept of "compounds represented by formula (1) and / or compounds represented by formula (2)" may be referred to as "specific compounds."

[0011] [Oil-repellent surface treatment composition of the present invention] The oil-repellent surface treatment composition of the present invention (the composition of the present invention) will be described below. The composition of the present invention, This is an oil-repellent surface treatment composition comprising a compound represented by formula (1) and / or a compound represented by formula (2) as a solute component. [ka] In formula (1), Each X independently represents either O or a single bond. Q1 independently represents a single bond or a divalent organic group. Q2 represents a single bond or a (p+q) valence linking group. Y independently represents either -COOH or -SO3H. p and q each independently represent numbers from 1 to 3. m represents 1 through 5. [ka] In formula (2), Each X independently represents either O or a single bond. Q1 independently represents a single bond or a divalent organic group. Q2 independently represents either a single bond or a (p+1) valence linking group. n represents 1 to 2, p represents 1 to 3, m represents 1 through 5.

[0012] Even if formulas (1) and / or (2) contained in the composition of the present invention are unexpectedly released into the environment, the decomposition products resulting from the decomposition of formulas (1) and / or (2) have a short chain length (1 carbon atom) in the perfluoroalkyl group, so their accumulation in living organisms is very low. For this reason, the composition of the present invention is considered to have a low environmental impact.

[0013] [Compound represented by formula (1)] The compounds represented by formula (1) that can be included as solute components in the composition of the present invention are as follows: [ka] In formula (1), Each X independently represents either O or a single bond. Q1 independently represents a single bond or a divalent organic group. Q2 represents a single bond or a (p+q) valence linking group. Y independently represents either -COOH or -SO3H. p and q each independently represent numbers from 1 to 3. m represents 1 through 5.

[0014] [X] In equation (1), X represents either an oxygen atom (O) or a single bond, independently. In formula (1), X is preferably O (oxygen atom) from the viewpoint of achieving superior effects (lower environmental concerns) in the present invention. When X in formula (1) is O (oxygen atom), that is, when formula (1) has a trifluoromethoxy group, even if released into the environment, the CF3OH that can be produced from the trifluoromethoxy group by the decomposition of formula (1) is an unstable compound and decomposes easily in the environment (for example, at temperatures above -20°C). Therefore, compounds in formula (1) where X is O (oxygen atom) can significantly reduce the risk of persistence in the environment and long-distance travel.

[0015] [Q1] In formula (1), Q1 independently represents either a single bond or a divalent organic group. In formula (1), Q1 is preferably a single bond from the viewpoint of oil repellency.

[0016] (Divalent organic group) Examples of divalent organic groups as Q1 include divalent hydrocarbon groups, specifically alkylene groups, alkenylene groups, alkylylene groups, and divalent aromatic hydrocarbon groups. In divalent hydrocarbon groups, some of the carbon atoms constituting them may be replaced by oxygen atoms. Examples of the alkylene groups mentioned above include methylene groups and ethylene groups.

[0017] [Q2] In formula (1), Q2 represents a single bond or a (p+q) valence linking group.

[0018] ((p+q) valence linking group) Examples of (p+q) valency linking groups as Q2 include (p+q) valency hydrocarbon groups. (p+q) valent hydrocarbon group Examples of (p+q) valency hydrocarbon groups include, for example, groups obtained by removing (p+q) hydrogen atoms from aliphatic hydrocarbons (aliphatic hydrocarbons include linear, branched, cyclic, and combinations thereof; aliphatic hydrocarbons may have unsaturated bonds), and groups obtained by removing (p+q) hydrogen atoms from aromatic hydrocarbons. A (p+q) valent hydrocarbon group may have some of its constituent carbon atoms replaced by oxygen atoms.

[0019] (Combination of Q1 and Q2) Examples of combinations of Q1 and Q2 in equation (1) include combinations where both Q1 and Q2 are single bonds (in this case, p=q=1), and combinations where Q1 is a single bond and Q2 is an alkylene group (in this case, p=q=1).

[0020] [Y] In equation (1), Y independently represents either -COOH or -SO3H.

[0021] [p] In equation (1), p represents 1 to 3. From the viewpoint of excellent adhesion, p is preferably 1.

[0022] [q] In equation (1), q represents 1 to 3. One preferred embodiment is that q is 1.

[0023] [m] In equation (1), m (the number of CF3-X units) represents 1 to 5. One preferred embodiment is that m is 1.

[0024] [CF3-X- group] In formula (1), the bonding positions of the m CF3-X- groups on the benzene ring are not particularly limited. One preferred embodiment is that any one of the m CF3-X- groups is bonded to the p-position of the benzene ring relative to Q1.

[0025] Examples of compounds in formula (1) where Y is -SO3H include the following formulas (1-4) to (1-5). [ka] In the above formulas (1-4), the trifluoromethyl group may be bonded to the ortho, meta, or para position of benzenesulfonic acid, but it is preferable that it be bonded to the para position of benzenesulfonic acid. [ka] In the above formulas (1-5), the trifluoromethoxy group may be bonded to the ortho, meta, or para position of benzenesulfonic acid, but it is preferable that it be bonded to the para position of benzenesulfonic acid.

[0026] (Preferred embodiment of formula (1)) With respect to formula (1), specific examples of preferred structures that offer superior effects of the present invention are shown below [Formulas (1-1) to (1-3)]. [ka] In the above formula (1-1), the trifluoromethyl group may be bonded to the ortho, meta, or para position of benzoic acid, but it is preferable that it be bonded to the para position of benzoic acid. [ka] In the above formula (1-2), the trifluoromethoxy group may be bonded to the ortho, meta, or para position of benzoic acid, and it is preferable that it be bonded to the para position of benzoic acid. [ka] In the above formulas (1-3), the trifluoromethoxy group may be bonded to the ortho, meta, or para position of phenylacetic acid, but it is preferable that it be bonded to the para position of phenylacetic acid.

[0027] [Compound represented by formula (2)] The compounds represented by formula (2) that can be included as solute components in the composition of the present invention are as follows: [ka] In formula (2), Each X independently represents either O or a single bond. Q1 independently represents a single bond or a divalent organic group. Q2 independently represents either a single bond or a (p+1) valence linking group. n represents 1 to 2, p represents 1 to 3, m represents 1 through 5.

[0028] [X] In equation (2), X independently represents either O (oxygen atom) or a single bond. In formula (2), X is preferably O (oxygen atom) from the viewpoint of achieving superior effects (lower environmental concerns) in the present invention. When X in formula (2) is O (oxygen atom), that is, when formula (2) has a trifluoromethoxy group, even if released into the environment, the CF3OH that can be produced from the trifluoromethoxy group by the decomposition of formula (2) is an unstable compound and decomposes easily in the environment (for example, at temperatures above -20°C). Therefore, compounds in formula (2) where X is O (oxygen atom) can significantly reduce the risk of persistence in the environment and long-distance travel.

[0029] [Q1] In formula (2), Q1 independently represents either a single bond or a divalent organic group. In formula (2), Q1 is preferably a single bond from the viewpoint of oil repellency.

[0030] (Divalent organic group) Examples of divalent organic groups as Q1 include divalent hydrocarbon groups, specifically alkylene groups, alkenylene groups, alkylylene groups, and divalent aromatic hydrocarbon groups. In divalent hydrocarbon groups, some of the carbon atoms constituting them may be replaced by oxygen atoms. Examples of the alkylene groups mentioned above include methylene groups and ethylene groups.

[0031] [Q2] In equation (2), Q2 independently represents either a single bond or a (p+1) valence linking group.

[0032] ((p+1) valence linking group) Examples of (p+1) valent linking groups for Q2 include (p+1) valent hydrocarbon groups and oxygen atoms. (p+1) valent hydrocarbon group Examples of (p+1) valency hydrocarbon groups include, for example, groups obtained by removing (p+1) hydrogen atoms from aliphatic hydrocarbons (aliphatic hydrocarbons include linear, branched, cyclic, and combinations thereof; aliphatic hydrocarbons may have unsaturated bonds), and groups obtained by removing (p+1) hydrogen atoms from aromatic hydrocarbons. A (p+1) valent hydrocarbon group may have some of its constituent carbon atoms replaced by oxygen atoms.

[0033] (Combination of Q1 and Q2) Examples of combinations of Q1 and Q2 in equation (2) include a combination where Q1 is a single bond and Q2 is an oxygen atom (in this case, p=1), and a combination where Q1 is a single bond and Q2 is an alkylene group (in this case, p=1).

[0034] [n] In equation (2), n represents a range from 1 to 2. n is preferably 1 from the viewpoint of excellent adhesion.

[0035] [p] In equation (2), p (lowercase p) represents 1 to 3. One preferred embodiment is that p is 1.

[0036] [m] In equation (2), m (the number of CF3-X units) represents 1 to 5. One preferred embodiment is that m is 1.

[0037] [CF3-X- group] In formula (2), the bonding positions of the m CF3-X- groups on the benzene ring are not particularly limited. One preferred embodiment is that any one of the m CF3-X- groups is bonded to the p-position of the benzene ring relative to Q1.

[0038] (Preferred embodiment of formula (2)) With respect to formula (2), from the viewpoint of achieving superior effects of the present invention, it is preferable that in formula (2), X is an oxygen atom, m=p=n=1, and Q1 is a single bond and Q2 is an oxygen atom, or Q1 is a single bond and Q2 is an alkylene group. Specific examples of more preferable structures are shown below. [ka] [ka]

[0039] (Manufacturing method of formula (2)) Examples of manufacturing methods for formula (2) include the following: (Manufacturing method, part 1) When Q2 in equation (2) is an oxygen atom • Preparation of precursors A compound represented by formula (a1) below, such as 4-trifluoromethoxyphenol or 4-trifluoromethylphenol, is dissolved in a solvent and cooled to, for example, -30°C to +10°C. After adding the catalyst dropwise in an amount of 1 to 5 molar equivalents relative to the compound represented by formula (a1), the dialkyl halogenated phosphate is added dropwise in an amount of 1 to 5 molar equivalents relative to the compound represented by formula (a1) while maintaining the temperature to, for example, -30°C to +10°C. After the dropwise addition is complete, the temperature is raised to room temperature and the mixture is stirred. The reaction mixture is analyzed, for example by GC, to confirm that the compound represented by formula (a1) has been consumed, and the reaction mixture is purified to obtain a compound represented by formula (a2) below, such as O,O-diethyl-p-trifluoromethoxyphenyl-phosphate (precursor).

[0040] Examples of the solvents mentioned above include dichloromethane, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and butyl acetate. Examples of the catalysts mentioned above include triethylamine, triethylenediamine, and 1,4-diazabicyclo[2.2.2]octane. Examples of alkyl groups in the above-mentioned halogenated dialkyl phosphate include alkyl groups having 1 to 10 carbon atoms. Examples of the above-mentioned halogenated dialkyl phosphate include diethyl chlorophosphate, dimethyl chlorophosphate, diisopropyl chlorophosphate, 2-chloro-2-oxo-1,3,2-dioxaphosphoran, and diphenyl chlorophosphate.

[0041] [ka]

[0042] In equation (a1), X, m, and Q1 are the same as in equation (2). In formula (a2), X, m, Q1, and n are the same as in formula (2). In formula (a2), p is 1. In formula (a2), R is the same as the alkyl group of the above-mentioned dialkyl halogenated phosphate.

[0043] Reaction of formula (a2) with trialkylsilane halogens As described above, the compound represented by formula (a2) obtained as a precursor is dissolved in a solvent and cooled to, for example, -30°C to +10°C. A trialkylsilane halide is added dropwise in an amount of 1 to 5 molar equivalents relative to the compound represented by formula (a2), while maintaining the temperature to, for example, -30°C to +10°C. After the addition is complete, the temperature is raised to room temperature and the mixture is stirred. The reaction solution is analyzed, for example by GC, to confirm that the compound represented by formula (a2) has been consumed, and a compound represented by the following formula (a3), such as O,O-di(trimethylsilyl)-p-trifluoromethoxyphenyl-phosphate (intermediate), is obtained.

[0044] Examples of the solvents mentioned above include acetonitrile, dichloromethane, diethyl ether, and tetrahydrofuran. Examples of alkyl groups in the above-mentioned halogenated trialkylsilane include alkyl groups having 1 to 10 carbon atoms. Examples of the above-mentioned halogenated trialkylsilane include bromotrimethylsilane, chlorotrimethylsilane, iodotrimethylsilane, and chlorotriethylsilane.

[0045] [ka]

[0046] In formula (a3), X, m, Q1, and n are the same as in formula (2). In formula (a3), p is 1. In formula (a3), R is the same as the alkyl group of the above-mentioned halide trialkylsilane.

[0047] • Hydrolysis reaction of formula (a3) The compound represented by formula (a3) ​​obtained as described above is cooled to, for example, -30°C to +10°C, and methanol, ethanol, water, or an alcohol / water mixture such as methanol or ethanol is added dropwise to the compound represented by formula (a3). The reaction mixture is heated to room temperature and stirred. The reaction mixture is analyzed, for example by GC, to confirm that the compound represented by formula (a3) ​​has been consumed, and the reaction mixture is purified to obtain a compound represented by formula (2-3), such as p-trifluoromethoxyphenyl phosphate, as the compound represented by formula (2). [ka]

[0048] In equation (2-3), X, m, Q1, and n are the same as in equation (2). In equation (2-3), p is 1.

[0049] (Manufacturing method, part 2) When Q2 in formula (2) is a (p+1) valent hydrocarbon group Reaction of formula (b1) with trialkyl phosphite A compound represented by formula (b1) below (1 molar equivalent), such as 4-(trifluoromethoxy)benzyl chloride, is mixed with a trialkyl phosphite such as triethyl phosphite (1-2 molar equivalents). The mixture is then heated at room temperature to 180°C and stirred to complete the reaction. After the reaction, the reaction mixture is allowed to return to room temperature, and then the excess trialkyl phosphite is removed from the reaction mixture under reduced pressure to obtain the compound represented by formula (b2).

[0050] [ka] In equation (b1), X, m, Q1, and p are the same as in equation (2), and Q 21 This is similar to the (p+1) valency hydrocarbon group as Q2 in formula (2), and Z represents a halogen atom such as a chlorine atom or a bromine atom. Note that if the compound represented by formula (b1) is 4-(trifluoromethoxy)benzyl chloride, then in formula (b1), m=1, Q1=single bond, Q21 = Methylene group, p=1, Z=chlorine atom. In equation (b2), X, m, Q1, p, and n are the same as in equation (2). Q in equation (b2) 21 This is the same as the (p+1) valent hydrocarbon group as Q2 in formula (2). R in formula (b2) is the same as the alkyl group possessed by the above trialkyl phosphite.

[0051] • Hydrolysis reaction of formula (b2) To 10 parts of the compound represented by formula (b2) obtained as described above, 50 to 100 parts of hydrochloric acid and 1 to 10 parts of an alcohol such as ethanol are added, and the mixture is heated under conditions of 80 to 120°C while stirring, and then slowly refluxed. After completing the hydrolysis reaction of the phosphate ester portion in formula (b2), the reaction mixture is cooled. By filtering and drying the precipitate formed in the reaction mixture, a phosphate compound represented by formula (2) can be obtained as the compound represented by formula (2) below, and also as the phosphate compound represented by formula (2-4).

[0052] [ka]

[0053] In equation (2-4), X, m, Q1, p, and n are the same as in equation (2). Q in equation (2-4) 21 This is similar to the (p+1) valent hydrocarbon group as Q2 in formula (2).

[0054] (Concentration of specific compounds) The concentration of the compound represented by formula (1) or formula (2) in the composition of the present invention is not particularly limited, but for example, the concentration of the compound represented by formula (1) or formula (2) in the composition of the present invention can be 0.01 to 20% by mass. When the composition of the present invention contains compounds represented by formula (1) and formula (2), the concentrations of the compounds represented by formula (1) and formula (2) in the composition of the present invention (the total concentration thereof) are not particularly limited, but can be, for example, 0.02 to 20% by mass in the composition of the present invention. Furthermore, if the compound represented by formula (1) or the compound represented by formula (2) forms a salt with a base described later, the amount of the base that forms the salt is not included in the concentration of the specific compound described above.

[0055] (solvent) In addition to the compound represented by formula (1) and / or the compound represented by formula (2) as solute components, a preferred embodiment of the composition of the present invention includes a solvent. The solvents that may be included in the composition of the present invention are not particularly limited as long as they can disperse and / or dissolve the specific compound. Examples of solvents include fluorinated solvents; hydrocarbon organic solvents; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; and aqueous solvents.

[0056] Fluorine-based solvents Examples of fluorinated solvents include hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs). Specific examples of fluorinated solvents are shown below, but the term "fluorinated solvent" is not limited to these.

[0057] m-xylenehexafluoride p-xylenehexafluoride CF3CH2CF2CH3 CF3CH2CF2H C6F 13 OCH3 C6F 13 OC2H5 C6F 13 CH2 CH3 C3F7OCH3 C3F7OC2H5 C6F 13 H CF2HCF2CH2OCF2CF2H CF3CFHCFHCF2CH3 CF3(OCF2CF2) n (OCF2) m OCF2H C8F 17 OCH3 C7F 15 OCH3 C7F 13 OCH3 C4F9OCH3 C4F9OC2H5 C4F9CH2CH3 CF3CH2OCF2CF2CF2H CF3CF(CH2CF3)CF(OCH3)CF2CF3 CF2HCF2OCH2CF3(AE - 3000) (In the above examples, the subscripts m and n each independently represent an integer from 1 to 20.) And mixtures thereof Examples of the mixture include a mixture of CF3(CF2)3OC2H5 and (CF3)2CFCF2OC2H5, which are isomers of C4F9OCH2CH3 (ethyl nonafluorobutyl ether).

[0058] ·Hydrocarbon-based organic solvents Examples of hydrocarbon-based organic solvents include aromatic hydrocarbons such as xylene, toluene, and ethylbenzene; alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane; and chain aliphatic hydrocarbons such as hexane, heptane, octane, and decane.

[0059] ·Aqueous solvents Examples of aqueous solvents include water or a mixture of water and alcohol. Examples of the alcohol include isopropanol, 1-propanol, ethanol, methanol, etc.

[0060] When the composition of the present invention contains an aqueous solvent as a solvent, one preferred embodiment is that the main component of the aqueous solvent is water. In this specification, the main component of an aqueous solvent is water, which means that the water content in the total amount of the aqueous solvent is 50 to 100% by mass.

[0061] (Non-flammable) In one preferred embodiment, the solvent that may be included in the composition of the present invention is a non-flammable solvent. Examples of non-flammable solvents include the fluorine-based solvents and aqueous solvents mentioned above.

[0062] (Solvent content) If the composition of the present invention contains a solvent, the amount of solvent is not particularly limited, as long as it is sufficient to disperse and / or dissolve the specific compound. If the composition of the present invention contains a solvent and further contains a base as described later, the amount of solvent is not particularly limited, as long as it is in an amount that can disperse and / or dissolve the specific compound and the base.

[0063] (base) In order to improve the solubility of specific compounds in the composition of the present invention, one preferred embodiment is that the composition further contains a base. If the composition of the present invention further contains a base, the base is Y in formula (1) or [-P(=O)(OH) in formula (2) that the specific compound has 3-n It can form a salt with ] (hereinafter also simply referred to as "phosphate group") (the above base becomes Y or the counterion of the above phosphate group), and can improve the solubility of specific compounds in the composition of the present invention. Examples of the above-mentioned bases include compounds containing alkali metals such as sodium and potassium (specifically, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate); compounds containing alkaline earth metals such as magnesium and calcium (specifically, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide); ammonia; and organic amines such as diethanolamine and triethylamine.

[0064] • Salt of the compound represented by formula (1) In a preferred embodiment, the salt of the compound represented by formula (1) is a salt of the compound represented by formula (1) and a base. Examples of salts of the compound represented by formula (1) with a base include sodium salts, potassium salts, ammonium salts, and triethylammonium salts of the compounds represented by formulas (1-1) to (1-5), and magnesium salts and calcium salts of the compounds represented by formulas (1-1) to (1-5).

[0065] • Salt of the compound represented by formula (2) A preferred embodiment is that the salt of the compound represented by formula (2) is a salt of the compound represented by formula (2) and a base. Examples of salts of the compound represented by formula (2) with a base include sodium salts, potassium salts, ammonium salts, and triethylammonium salts of the compounds represented by formulas (2-1) to (2-2) above, and magnesium salts and calcium salts of the compounds represented by formulas (2-1) to (2-1) above.

[0066] • Amount of base used Furthermore, the use of the above-mentioned base is intended to improve the dispersibility and / or solubility of the specific compound used in the present invention in the solvent. For this reason, the amount of base used is not particularly limited, as long as it does not impair the dispersion stability of the specific compound used in the present invention or the liquid stability of the oil-repellent surface treatment composition of the present invention due to precipitation of the base used.

[0067] (Additives) The composition of the present invention may further contain, as necessary, a pH adjuster, a rust inhibitor, a dye, a flame retardant, an antifoaming agent, or an antistatic agent, to the extent that it does not impair the effects of the present invention.

[0068] (Method for preparing the composition of the present invention) For example, the composition of the present invention can be prepared by mixing a specific compound, a solvent, and a base and additives, which may be included as needed.

[0069] (Method of Using the Composition of the Present Invention) Examples of the method of using the composition of the present invention include, for example, a method of applying the composition of the present invention to a substrate. By the above application, a layer of a surface treatment agent (a layer made of a specific compound) can be formed on the surface of the substrate, and the oil repellency of the surface of the substrate can be improved. Further, by the above application, excellent oil repellency can be further imparted to the surface of the substrate. The method of applying the composition of the present invention to a substrate is not particularly limited. Examples include coating, dipping, etc. After applying the composition of the present invention to a substrate, for example, the solvent can be dried under the conditions of 10 to 120 °C.

[0070] Examples of the material of the substrate include glass, plastic, rubber, metal, ceramic, etc. Specific examples of the substrate include molded products around water such as bathroom members, wash face members, and kitchen members; daily necessities such as umbrellas, shoes, and bags; exterior decoration related to buildings such as bridge piers, roofs, and outer walls; interior decoration related to floors and inner walls; housing supplies such as furniture and household appliances; vehicle bodies (including exterior materials and interior materials) such as ships, airplanes, and automobiles; electronic substrates, and other industrial products and parts (sensors, electronic components, filters, etc.).

Example

[0071] The present invention will be described in more detail with reference to the following examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below. In the following, unless otherwise specified, those indicated by "parts" and "%" are "parts by mass" and "% by mass". Regarding the compounds used as raw materials, etc. in this example, unless otherwise specified, the above compounds were obtained from the market.

[0072] <Measurement of NMR> NMR( 1 H-NMR,19 F-NMR, 31 The measurement of (F-NMR, 31 P-NMR) is shown below. The measurement target substance was dissolved in the heavy solvent methanol-d4, and prepared so that the concentration of the measurement target substance was about 1% by mass. The prepared solution was transferred to a measurement tube for NMR. In addition, a small amount of a reference substance was added for the measurement of each nuclide. The measurement conditions are shown below. Apparatus: JNM-ECZ400R / S1 (manufactured by JEOL Ltd., 400 MHz) Nuclide: 1 [[ID=巧]]H-NMR (standard: hexamethyldisiloxane, frequency 400 MHz), 19 F-NMR (standard: m-xylene hexafluoride, frequency 376 MHz), 31 P-NMR (standard: phosphoric acid, frequency 162 MHz) Number of integrations: 32

[0073] <Measurement by GC> The measurement by GC (gas chromatography) is shown below. Apparatus: GC-2014 (manufactured by Shimadzu Corporation) Column: DB-5 (manufactured by Agilent Technologies, Inc.) (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm) Inlet temperature: 250 °C Injection method: Split Split ratio: 50 Column temperature program: Hold at 50 °C for 5 minutes, raise the temperature to 250 °C at 10 °C / min, and hold at 250 °C for 10 minutes

[0074] [Synthesis of Precursor 1: O,O-Diethyl-p-trifluoromethoxyphenyl-phosphate] In a four-necked flask, 3.45 g of 4-trifluoromethoxyphenol (0.0194 mol) was dissolved in 96.87 g of dichloromethane and cooled to below 5°C by immersion in ice water. Triethylamine (9.80 g, 0.0969 mol) was added dropwise, and while maintaining the temperature below 5°C, diethyl chlorophosphate (8.36 g, 0.0969 mol) was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and stirred overnight. The reaction mixture was analyzed by GC to confirm that 4-trifluoromethoxyphenol had been consumed, and washed with saturated sodium bicarbonate. The resulting organic layer was washed with 1N hydrochloric acid and water, and the organic layer was dried over anhydrous magnesium sulfate. The dried organic layer was filtered, and the resulting filtrate was concentrated to obtain 9.04 g of crude product containing O,O-diethyl-p-trifluoromethoxyphenyl phosphate (GC area %: 77.2%).

[0075] [Preparation Example 1: Synthesis of p-trifluoromethoxyphenyl phosphate] The crude product (8.86 g) containing O,O-diethyl-p-trifluoromethoxyphenyl phosphate obtained in precursor 1 was dissolved in acetonitrile and cooled to below 5°C by immersion in ice water. Bromotrimethylsilane (5.93 g, 0.0775 mol) was slowly added dropwise while maintaining the temperature below 5°C. After the addition was complete, the temperature was raised to room temperature and stirred overnight. The reaction mixture was analyzed by GC to confirm that O,O-diethyl-p-trifluoromethoxyphenyl phosphate had been consumed, and the mixture was concentrated to obtain a crude product containing O,O-di(trimethylsilyl)-p-trifluoromethoxyphenyl phosphate. The mixture was immersed in ice water and cooled to below 5°C, and a methanol / water mixture (20g / 25g) was added dropwise. The mixture was heated to room temperature and stirred overnight. The reaction solution was analyzed by GC to confirm that O,O-di(trimethylsilyl)-p-trifluoromethoxyphenyl-phosphate had been consumed, and the mixture was concentrated to obtain the crude product of p-trifluoromethoxyphenyl-phosphate. Toluene (60g) was added to this crude product, and the temperature was raised to 80°C until complete melting occurred. After cooling to room temperature, the obtained crystals were filtered off and dried under reduced pressure to obtain 1.68g of the target p-trifluoromethoxyphenyl-phosphate (formula (2-1) below) (NMR purity: 94.8%). [ka]

[0076] The compound ultimately produced in Preparation Example 1 1 The 1H-NMR chart is shown in Figure 1. In Figure 1, a chemical shift of δ = 7.19-7.24 (m, 4H) was observed. The compound ultimately produced in Preparation Example 1 19 The F-NMR chart is shown in Figure 2. In Figure 2, a chemical shift of δ = -59.3 (s, 3F) was observed. The compound ultimately produced in Preparation Example 1 31 The P-NMR chart is shown in Figure 3. In Figure 3, a chemical shift of δ = -6.20 (s, 1P) was observed. From the NMR results above, it was confirmed that the compound ultimately produced in Preparation Example 1 was the compound represented by formula (2-1) above.

[0077] [Preparation of composition] Each composition was prepared by mixing the solutes and solvents shown in Tables 1-3. Specifically, in Table 1, the composition was prepared by mixing the solute (formula (1-1-1)) shown in the solute column of Example 1 with solvent 1. The same procedure was followed for Examples 2-4 and Comparative Examples 1-5. In Table 2, the composition was prepared by mixing the solute (formula (1-1-1)) shown in the solute column of Example 1 with solvent 2. The same procedure was followed for Examples 2-4 and Comparative Examples 1-5. In Table 3, the composition was prepared by mixing the solute (formula (1-1-1)) shown in the solute column of Example 1 with solvent 3. The same procedure was followed for Examples 2-4 and Comparative Examples 1-5. When solvent 1 or 2 was used, the concentration of the solute in the composition was 1% by mass. When solvent 3 was used, the concentration of the solute in the composition was 2% by mass. When solvent 2 was used, triethylamine was further used as a base, and the composition was obtained by mixing the solute, solvent 2, and triethylamine as a base. The amount of triethylamine used was 1% by mass of the total composition. When solvent 3 was used, ammonia was further used as a base, and the composition was obtained by mixing the solute, solvent 3, and ammonia as a base. The amount of ammonia used was 0.6% by mass of the total composition. In this specification, when a base is used with respect to a solute, the amount of the base is not included in the concentration of the solute.

[0078] [evaluation] <Preparation of evaluation test specimens> As described above, glass plates were immersed in each composition for 1 minute. After removing the glass plates from the compositions, if the composition contained solvents 1 and 2, the glass plates were dried at room temperature (25°C) for 20 minutes, and if the composition contained solvent 3, the glass plates were dried at 120°C for 5 minutes to obtain evaluation test pieces.

[0079] <Measuring Contact Angle> n-hexadecane (n-HD) was dropped onto the evaluation test specimens obtained as described above, and the contact angle (in degrees) of n-hexadecane (n-HD) was measured using a contact angle meter DMo-501 (manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of n-hexadecane was measured at five points, and the average was used as the evaluation value. The evaluation results are shown in Tables 1 to 3.

[0080] <Evaluation Criteria for Oil Repellency> In the present invention, regardless of which of the above solvents 1 to 3 is used, if the contact angle of the resulting n-hexadecane is 35 degrees or higher, then it is considered to have excellent oil repellency. The greater the contact angle (greater than 35 degrees), the better the oil-repellent properties. A contact angle of 40 degrees or more is preferable from the viewpoint of further improving oil repellency. If the solute did not dissolve in the solvent, this result was indicated as "slowly soluble" in Tables 1-3. Note that the contact angle was not measured when the solute did not dissolve in the solvent. Furthermore, for Comparative Examples 1 and 2, the contact angles when using solvents 1 and 2 were 35 degrees or less, so the contact angle when using solvent 3 was not measured. For Comparative Example 5, the contact angle when using solvent 1 was 35 degrees or less, so the contact angles when using solvents 2 and 3 were not measured. In cases where the contact angle was not measured as described above, this is indicated by "-" in Tables 2 and 3.

[0081] <Evaluation Criteria for Low Environmental Concerns> In this invention, when the fluorine compound included as a solute component has a perfluoroalkyl group (CF3X group) consisting of a trifluoromethoxy group or a trifluoromethyl group, the resulting composition was evaluated as having low environmental concerns. When the perfluoroalkyl group is a trifluoromethoxy group, the resulting composition is preferable as it poses even lower environmental concerns. Furthermore, even when the solute component is a hydrocarbon compound that does not contain fluorine, the resulting composition was evaluated as having low environmental concerns.

[0082] [Table 1]

[0083] [Table 2]

[0084] [Table 3]

[0085] (Solvents in Table 1) • Solvent 1 (IPA): Isopropanol (Solvents and bases in Table 2) • Solvent 2 (AE-3000): Product name Asahi Clean AE-3000 (manufactured by AGC Corporation). CF2HCF2OCH2CF3. As described above, when using solvent 2, triethylamine was further used as a base, and the composition was obtained by mixing the solute, solvent 2, and triethylamine. The amount of triethylamine used was 1% by mass of the total composition. The concentration of the solute in the composition when solvent 2 was used was 1% by mass. (Solvents and bases in Table 3) • Solvent 3 (aqueous solvent): 77.4% by mass of water, 20% by mass of isopropanol, and 0.6% by mass of ammonia as a base. Note that the amounts of each component in Solvent 3 are the amounts in the total composition. When Solvent 3 was used, the concentration of the solute in the composition was 2% by mass.

[0086] (Solutes in Tables 1-3) Formula (1-1-1): 4-(trifluoromethyl)benzoic acid (structure shown below), manufactured by Tokyo Chemical Industry Co., Ltd. [ka] Formula (1-1-1) corresponds to the compound represented by formula (1) in the present invention. In Example 1 of Table 1, the mixture obtained by mixing solvent 1 with the above formula (1-1-1) (without a base) contains the above formula (1-1-1) as a solute. The above formula (1-1-1) was dissolved in solvent 1. Furthermore, in Example 1 of Table 2, the solute of the mixture obtained by mixing solvent 2 with the above formula (1-1-1) and triethylamine (base) is considered to be a salt of formula (1-1-1) and triethylamine. Similarly, in Example 1 of Table 3, the solute of the mixture obtained by mixing solvent 3 with formula (1-1-1) and ammonia (base) is considered to be a salt of formula (1-1-1) and ammonia. The reason for this is that, in solvents 2 and 3, when no base is present, formula (1-1-1) disperses in solvents 2 and 3, but its solubility in solvents 2 and 3 is low. However, when a base is present in solvent 2 or solvent 3, the solubility of the solute, formula (1-1-1), increases.

[0087] Formula (1-2-1): 4-(trifluoromethoxy)benzoic acid (structure shown below), manufactured by Tokyo Chemical Industry Co., Ltd. [ka] Formula (1-2-1) corresponds to the compound represented by formula (1) in the present invention. In Example 2 of Table 1, the mixture obtained by mixing solvent 1 with the above formula (1-2-1) (without a base) contains the above formula (1-2-1) as a solute. The above formula (1-2-1) was dissolved in solvent 1. Furthermore, in Example 2 of Table 2, the solute of the mixture obtained by mixing solvent 2 with the above formula (1-2-1) and triethylamine (base) is considered to be a salt of formula (1-2-1) and triethylamine. Similarly, in Example 2 of Table 3, the solute of the mixture obtained by mixing solvent 3 with formula (1-2-1) and ammonia (base) is considered to be a salt of formula (1-2-1) and ammonia. The reason for this is that when no base is present in solvent 2 or solvent 3, formula (1-2-1) disperses in solvent 2 or solvent 3, but its solubility in solvent 2 or solvent 3 is low. However, when a base is present in solvent 2 or solvent 3, the solubility of the solute, formula (1-2-1), increases.

[0088] Formula (1-3-1): 4-(trifluoromethoxy)phenylacetic acid (structure shown below), manufactured by Tokyo Chemical Industry Co., Ltd. [ka] Formula (1-3-1) corresponds to the compound represented by formula (1) in the present invention. In Example 3 of Table 1, the mixture obtained by mixing solvent 1 with the above formula (1-3-1) (without a base) contains the above formula (1-3-1) as a solute. The above formula (1-3-1) was dissolved in solvent 1. Furthermore, in Example 3 of Table 2, the solute of the mixture obtained by mixing solvent 2 with the above formula (1-3-1) and triethylamine (base) is considered to be a salt of formula (1-3-1) and triethylamine. Similarly, in Example 3 of Table 3, the solute of the mixture obtained by mixing solvent 3 with formula (1-3-1) and ammonia (base) is considered to be a salt of formula (1-3-1) and ammonia. The reason for this is that, in solvent 2 or solvent 3, when no base was present, formula (1-3-1) dispersed in solvent 2 or solvent 3, but its solubility in solvent 2 or solvent 3 was low. However, in Example 3, when a base was present in solvent 2 or solvent 3, the solubility of the solute, formula (1-3-1), increased.

[0089] • Formula (2-1): The compound represented by formula (2-1) prepared as described above. [ka] The compound represented by formula (2-1) above corresponds to the compound represented by formula (2) in the present invention. In Example 4 of Table 1, the mixture obtained by mixing solvent 1 with the above formula (2-1) (without a base) contains the above formula (2-1) as a solute. The above formula (2-1) was dissolved in solvent 1. Furthermore, in Example 4 of Table 2, the solute of the mixture obtained by mixing solvent 2 with the above formula (2-1) and triethylamine (base) is considered to be a salt of the above formula (2-1) and triethylamine. The reason for this is that, in solvent 2, when no base was present, formula (2-1) dispersed in solvent 2 but its solubility in solvent 2 was low. However, in Example 4, when a base was present in solvent 2, the solubility of the solute, formula (2-1), increased.

[0090] Mix 2% by mass of the compound represented by formula (2-1) as the solute, the above solvent 3 (77.4% by mass of water, 20% by mass of isopropanol), and 0.6% by mass of ammonia as the base, dry the resulting composition as described above, and measure the contact angle using the obtained evaluation test piece in the same manner as in <Measurement of Contact Angle> above. The contact angle is 35 degrees or greater.

[0091] Formula (Y1): 4-(trifluoromethoxy)aniline (structure shown below), manufactured by Tokyo Chemical Industry Co., Ltd. [ka] Formula (Y2): 4-(trifluoromethoxy)phenol (structure shown below), manufactured by Tokyo Chemical Industry Co., Ltd. [ka] Formula (Y3): 4-methylbenzoic acid (structure shown below), manufactured by Tokyo Chemical Industry Co., Ltd. [ka] Formula (Y4): 4-Methoxybenzoic acid (structure shown below), manufactured by Tokyo Chemical Industry Co., Ltd. [ka] Formula (Y5): Triethoxy(4-(trifluoromethyl)phenyl)silane (structure shown below), manufactured by Angene International. [ka]

[0092] Based on the results shown in Tables 1-3, it was confirmed that the composition of the present invention exhibits the desired effect.

[0093] On the other hand, Comparative Examples 1, 2, and 5, which contained compounds lacking any carboxyl group, -SO3H, or phosphate group, and Comparative Examples 3 and 4, which contained compounds lacking either a trifluoromethoxy group or a trifluoromethyl group, exhibited insufficient oil repellency.

Claims

1. An oil-repellent surface treatment composition comprising a compound represented by formula (1) and / or a compound represented by formula (2) as a solute component. 【Chemistry 1】 In formula (1), Each X independently represents either O or a single bond. Q １ Each of these independently represents a single bond or a divalent organic group. Q ２ This represents a single bond or a (p+q) valence linking group. Y is independently -COOH or -SO ３ Represents H, p and q each independently represent numbers from 1 to 3. m represents 1 through 5. 【Chemistry 2】 In formula (2), Each X independently represents either O or a single bond. Q １ Each of these independently represents a single bond or a divalent organic group. Q ２ Each of these independently represents a single bond or a (p+1) valence linking group. n represents 1 to 2, p represents 1 to 3, m represents 1 through 5.

2. The oil-repellent surface treatment composition according to claim 1, further comprising a base.

3. The oil-repellent surface treatment composition according to claim 1 or 2, wherein X in formula (1) and / or X in formula (2) is O.

4. Q in equation (1) １ and / or Q in formula (2) １ The oil-repellent surface treatment composition according to claim 1 or 2, wherein the bond is a single bond.

5. The oil-repellent surface treatment composition according to claim 1 or 2, comprising a solvent, wherein the solvent is non-flammable.

6. The oil-repellent surface treatment composition according to claim 1 or 2, comprising an aqueous solvent, wherein the main component of the aqueous solvent is water.

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