Phosphate compounds and their salts

Abstract

The object of this invention is to provide a novel compound having a trifluoromethoxy group and exhibiting excellent oil repellency. [Solution] A phosphate compound represented by the following formula and its salt. In the formula, Q1 independently represents a single bond or a divalent organic group, Q2 independently represents a (p+1) valent linking group, n represents 1 to 2, p represents 1 to 3, and m represents 1 to 5. JPEG2026046272000018.jpg1975

Description

[Technical Field]

[0001] This invention relates to phosphate compounds and salts thereof. [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 Initiative] [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 novel compound having a trifluoromethoxy group and exhibiting 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] A phosphate compound represented by the following formula (X). [ka] In formula (X), each Q1 independently represents a single bond or a divalent organic group, each Q2 independently represents a (p+1) valent linking group, n represents 1 to 2, p represents 1 to 3, and m represents 1 to 5. [2] [1] Salts of the phosphate compounds described above. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a novel compound having a trifluoromethoxy group and exhibiting excellent oil repellency. Furthermore, according to the present invention, a salt of the above compound can be provided. [Brief explanation of the drawing]

[0009] [Figure 1]Figure 1 is a 1H-NMR chart of the compound finally produced in Example 1. [Figure 2] Figure 2 is a 19F-NMR chart of the compound finally produced in Example 1. [Figure 3] Figure 3 is a 31P-NMR chart of the compound finally produced in 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 representative 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 including the numerical values described before and after "~" as the lower limit value and the upper limit value. In this specification, each component can be used alone or in combination of two or more. In this specification, when two or more of a certain component are used in combination, the "content" of that component means the total content of those two or more, unless otherwise specified. In this specification, the production method of each component is not particularly limited unless otherwise specified. For example, conventionally known methods can be mentioned. In this specification, the phosphate compound of the present invention and the salt of the present invention are also collectively referred to as "the compound of the present invention". In this specification, when the phosphate compound of the present invention or the salt of the present invention has more excellent oil repellency, it is also said that "the effect of the present invention is more excellent". In this specification, the compound represented by formula (*) may be simply referred to as "formula (*)". For example, the compound represented by formula (X1) may be simply referred to as "formula (X1)".

[0011] [Phosphate Compound of the Present Invention] Hereinafter, the phosphate compound of the present invention will be described. The phosphate compound of the present invention is a phosphate compound represented by the following formula (X). [ka] In formula (X), each Q1 independently represents a single bond or a divalent organic group, each Q2 independently represents a (p+1) valent linking group, n represents 1 to 2, p represents 1 to 3, and m represents 1 to 5.

[0012] Even if the phosphate compounds of the present invention are unexpectedly released into the environment, the CF3OH that can be produced from the trifluoromethoxy group by decomposition is an unstable compound and decomposes easily in the environment (for example, at temperatures above -20°C), thus significantly reducing the risk of persistence in the environment and long-distance travel. The phosphate compounds of the present invention are considered to have a low environmental impact. The same applies to the salts of the present invention described later.

[0013] [Q1] In formula (X), each Q1 independently represents either a single bond or a divalent organic group.

[0014] (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.

[0015] [Q2] In equation (X), each Q2 independently represents a (p+1) valence linking group.

[0016] ((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.

[0017] (Combination of Q1 and Q2) Examples of combinations between Q1 and Q2 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).

[0018] [n] In equation (X), n represents a range from 1 to 2. n is preferably 1 from the viewpoint of excellent adhesion.

[0019] [p] In equation (X), p (lowercase p) represents 1 through 3. One preferred embodiment is that p is 1.

[0020] [m] In formula (X), m (number of trifluoromethoxy groups) represents 1 to 5. One preferred embodiment is that m is 1.

[0021] [Trifluoromethoxy group] In formula (X), the bonding positions of the m CF3O-(trifluoromethoxy groups) on the benzene ring are not particularly limited. One preferred embodiment is that one of the m CF3O-(trifluoromethoxy groups) is bonded to the p-position of the benzene ring relative to Q1.

[0022] (Preferred embodiment of phosphoric acid compound) With respect to the phosphoric acid compound of the present invention, from the viewpoint of achieving superior effects of the present invention, it is preferable that in formula (X), m=p=n=1, and that Q1 is a single bond and Q2 is an oxygen atom, or that Q1 is a single bond and Q2 is an alkylene group. Specific examples of more preferable structures are shown below. [ka] [ka]

[0023] (Method for producing phosphorylated compounds) Examples of methods for producing the phosphoric acid compound of the present invention include the following methods. (Manufacturing method, part 1) When Q2 in equation (X) is an oxygen atom • Preparation of precursors A compound represented by formula (a1) below, such as 4-trifluoromethoxyphenol, 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).

[0024] 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.

[0025] [ka]

[0026] The values ​​of m and Q1 in equation (a1) are the same as those of m and Q1 in equation (X). In formula (a2), m, Q1, and n are the same as in formula (X). In formula (a2), p is 1. In formula (a2), R is the same as the alkyl group of the above-mentioned halogenated dialkyl phosphate.

[0027] 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.

[0028] 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.

[0029] [ka]

[0030] In formula (a3), m, Q1, and n are the same as in formula (X). In formula (a3), p is 1. In formula (a3), R is the same as the alkyl group of the above-mentioned halide trialkylsilane.

[0031] • 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 phosphate compound represented by formula (X), such as p-trifluoromethoxyphenyl phosphate, represented by formula (X3).

[0032] [ka]

[0033] In equation (X3), m, Q1, and n are the same as in equation (X). In equation (X3), p is 1.

[0034] (Manufacturing method, part 2) When Q2 in formula (X) 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).

[0035] [ka] In equation (b1), m, Q1, and p are the same as in equation (X), and Q 21 This is similar to the (p+1) valency hydrocarbon group as Q2 in formula (X), 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, Q 21 = Methylene group, p=1, Z=chlorine atom. In equation (b2), m, Q1, p, and n are the same as in equation (X). Q in equation (b2) 21 This is similar to the (p+1) valent hydrocarbon group as Q2 in formula (X). R in formula (b2) is the same as the alkyl group possessed by the above trialkyl phosphite.

[0036] • 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 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 phosphoric acid compound represented by formula (X) can be obtained, as well as a phosphoric acid compound represented by the following formula (X4).

[0037] [Chem.]

[0038] In formula (X4), m, Q1, p, and n are the same as m, Q1, p, and n in formula (X). Q in formula (X4) 21 is the same as the (p + 1)-valent hydrocarbon group as Q2 in formula (X).

[0039] [Salt] The salt of the present invention is a salt of the phosphoric acid compound represented by the above formula (X). The salt of the present invention is [-P(=O)(OH) 3-n (hereinafter this is also simply referred to as "phosphoric acid group"). is [-P(=O)(OH)(O - [[ID=2x4]])] or [-P(=O)(O - )2], and is a compound having a cation corresponding to the above [-P(=O)(OH)(O - )] or [-P(=O)(O<x - )2].

[0040] [Cation] The cation possessed by the salt of the present invention is not particularly limited. For example, alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as magnesium ions and calcium ions; ammonium ions; cations of organic amines such as diethanolammonium ions and triethylammonium ions can be mentioned.

[0041] The salt of the present invention is preferably a salt of the phosphoric acid compound represented by formula (X) and a base. ·Base 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.

[0042] (Method of salt production) One method for producing the salt of the present invention is to produce the salt by mixing the phosphate compound of the present invention with a base. The base used in producing the salt of the present invention is the same as described above. When mixing the phosphate compound of the present invention with the base, a solvent may also be used.

[0043] • Amount of base used When a base is used in the production of the salt of the present invention, the use of the base is for the purpose of improving the dispersibility and / or solubility of the phosphoric acid compound of the present invention in the solvent. For this reason, when the compound of the present invention is used, for example, as a surface treatment agent, the amount of base used is not particularly limited, as long as the dispersion stability of the phosphoric acid compound of the present invention and the liquid stability of the surface treatment agent are not impaired by the precipitation of the base used.

[0044] ·solvent The solvent that can be used in producing the salt of the present invention is not particularly limited as long as it can disperse and / or dissolve the phosphate compound and / or base of the present invention. Preferably, the solvent can disperse and / or dissolve the phosphate compound and / or base of the present invention. 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.

[0045] Fluorine-based solvents Examples of fluorinated solvents include hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs). Specific examples of fluorinated solvents are listed below, but the term "fluorinated solvent" is not limited to these.

[0046] 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 (Product name AE-3000) (In the above example, the subscripts m and n each independently represent integers from 1 to 20.) and mixtures of these Examples of mixtures include a mixture of CF3(CF2)3OC2H5 and (CF3)2CFCF2OC2H5, which are isomers of C4F9OCH2CH3 (ethyl nonafluorobutyl ether).

[0047] • Hydrocarbon organic solvents Examples of hydrocarbon organic solvents include aromatic hydrocarbons such as xylene, toluene, and ethylbenzene; alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane; and chain-like aliphatic hydrocarbons such as hexane, heptane, octane, and decane.

[0048] • Water-based solvents Examples of aqueous solvents include water or a mixture of water and alcohol. Examples of alcohols include isopropanol, 1-propanol, ethanol, methanol, and the like.

[0049] • Amount of solvent used The amount of solvent used in the production of the salt of the present invention is not particularly limited, as long as it is sufficient to adequately dissolve the phosphoric acid compound of the present invention and the base mixed therewith.

[0050] ·Temperature conditions etc. In the salt production method of the present invention, the temperature conditions when mixing the phosphate compound and the base of the present invention can be, for example, 5 to 60°C. In the salt production method of the present invention, the phosphate compound and the base of the present invention may be stirred under the above temperature conditions.

[0051] (Uses of the phosphate compounds and salts of the present invention) The phosphate compounds and salts of the present invention can be used (function) as, for example, surface treatment agents.

[0052] (Surface treatment agent) When the compounds of the present invention are used as surface treatment agents, examples of such agents include surface treatment agents containing the phosphoric acid compounds and / or salts of the present invention. The phosphate compounds that may be included in the above surface treatment agent are not particularly limited as long as they are phosphate compounds of the present invention. The salt of the phosphoric acid compound that may be included in the above surface treatment agent is not particularly limited as long as it is the salt of the present invention. The above surface treatment agent may further contain a solvent in addition to the phosphoric acid compound and / or salt of the present invention. The solvent is the same as the solvent that may be used in the production of the salt of the present invention.

[0053] (Non-flammable) In one preferred embodiment, the solvent that may further be included in the above surface treatment agent is a non-flammable solvent. Examples of non-flammable solvents include the fluorine-based solvent and the aqueous solvent mentioned above.

[0054] (Concentration of the compound of the present invention) The concentration of the compound of the present invention contained in the above surface treatment agent (if the compound of the present invention includes the phosphoric acid compound of the present invention and the salt of the present invention, the total amount thereof; the same applies hereinafter) is not particularly limited. The entire surface treatment agent described above may be the compound of the present invention. Furthermore, the concentration of the compound of the present invention in the surface treatment agent when it is manufactured can be set to 0.01 to 10% by mass. Furthermore, when using the above-mentioned surface treatment agent, the concentration of the compound of the present invention in the surface treatment agent can be set to 0.01 to 10% by mass. Note that the concentration of the compound of the present invention in the surface treatment agent does not include the amount of the base that forms the salt of the present invention (the same applies hereinafter). Furthermore, the concentration of the compound of the present invention in the surface treatment agent described above does not include the amount of base used in producing the salt of the present invention, or the amount of base used further as described later (the same applies hereinafter).

[0055] (Additives) The above surface treatment agent may further contain, as necessary, a pH adjuster, rust inhibitor, dye, flame retardant, defoamer, antistatic agent, or base, to the extent that it does not impair the effects of the present invention. If you wish to add the above additive to the above surface treatment agent, you can do so by adding the above additive to the above surface treatment agent. If you wish to dilute the above surface treatment agent, you can use the solvent described above to dilute it. If the above-mentioned surface treatment agent further contains a base in addition to the phosphoric acid compound and the salt of the present invention, the base that can be further contained is not particularly limited. For example, the same base as described above in the method for producing the salt of the present invention can be included.

[0056] • Amount of base If the above surface treatment agent contains the salt of the present invention as the compound of the present invention, the above surface treatment agent may also contain bases used in excess with respect to the phosphate compound of the present invention when obtaining the salt of the present invention, and / or cations derived from bases liberated from the salt of the present invention. The same applies if the above surface treatment agent further contains bases in addition to the phosphate compound of the present invention and the salt of the present invention. After manufacturing the above-mentioned surface treatment agent, the amount of base contained in the surface treatment agent is not particularly limited, as long as it does not adversely affect the dispersion stability of the surface treatment agent.

[0057] • Dilution The concentration of the compound of the present invention in the mixture obtained by diluting the above surface treatment agent with the above solvent can be, for example, 0.01 to 10% by mass of the mixture. Furthermore, the base content in the mixture obtained after diluting the surface treatment agent with the solvent can be, for example, 0.01 to 10% by mass of the mixture.

[0058] (Method of using the above surface treatment agent or mixture) One method of using the above-mentioned surface treatment agent or a mixture obtained by diluting the above-mentioned surface treatment agent as described above (hereinafter collectively referred to as "the above-mentioned surface treatment agent, etc.") is to apply the above-mentioned surface treatment agent, etc. to a substrate. By applying the above-mentioned agent, a layer of the surface treatment agent (a layer of the compound of the present invention) is formed on the surface of the substrate, and the oil repellency of the surface of the substrate can be improved. Furthermore, by applying the above-mentioned agent, excellent oil repellency can be further imparted to the surface of the substrate. The method for applying the above-mentioned surface treatment agent to the substrate is not particularly limited. For example, coating is one possible method. After applying the above surface treatment agent or the like to the substrate, for example, the solvent can be dried under the conditions of 10 to 120 °C.

[0059] Examples of the material of the substrate include glass, plastic, rubber, metal, ceramic, and the like. 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.).

Examples

[0060] 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 as long as they do not depart from the gist 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 expressed in "parts" and "%" are "parts by mass" and "mass %". Regarding the compounds used as raw materials and the like in this example, unless otherwise specified, the above compounds were obtained from the market.

[0061] <Measurement of NMR> NMR( 1 H-NMR, 19 F-NMR, 31 The measurement of P-NMR) is shown below. The measurement object substance was dissolved in the heavy solvent methanol-d4, and it was prepared so that the concentration of the measurement object substance became about 1 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 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

[0062] <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 mode: Split Split ratio: 50 Column temperature program: Hold at 50 °C for 5 minutes, increase the temperature to 250 °C at 10 °C / min, and hold at 250 °C for 10 minutes

[0063] [Synthesis of Precursor 1: O,O-Diethyl-p-trifluoromethoxyphenyl-phosphate] In a four-necked flask, 4-trifluoromethoxyphenol (3.45 g, 0.0194 mol) was dissolved in dichloromethane (96.87 g) and immersed in ice water and cooled to 5 °C or lower. After triethylamine (9.80 g, 0.0969 mol) was added dropwise, while maintaining the temperature at 5 °C or lower, 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 solution was analyzed by GC to confirm that 4-trifluoromethoxyphenol was consumed, and then washed with saturated sodium bicarbonate. The obtained 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 obtained filtrate was concentrated to obtain 9.04 g of a crude product containing O,O-diethyl-p-trifluoromethoxyphenyl-phosphate (GC area%: 77.2%).

[0064] 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. This was cooled to below 5°C by immersion in ice water, and a methanol / water mixture (20 g / 25 g) was added dropwise. The temperature was raised to room temperature and stirred overnight. The reaction mixture was analyzed by GC to confirm that O,O-di(trimethylsilyl)-p-trifluoromethoxyphenyl-phosphate was consumed, and the mixture was concentrated to obtain the crude product of p-trifluoromethoxyphenyl-phosphate. Toluene (60 g) was added to this crude product, and the temperature was raised to 80°C to completely melt it. After cooling to room temperature, the resulting crystals were filtered off and dried under reduced pressure to obtain 1.68 g of the target p-trifluoromethoxyphenyl-phosphate (formula (X1) below) (NMR purity: 94.8%). [ka]

[0065] The compound ultimately produced in 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 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 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 Example 1 was the compound represented by formula (X1).

[0066] [Preparation of the mixture] Each mixture was prepared by mixing the solute and solvent shown in Table 1. Specifically, each mixture (two different mixtures with different solvents) was prepared by mixing the compound (solute) represented by formula (X1) obtained in Example 1 with one of solvents 1 to 2. For Comparative Example 1, the solute (formula (Y1)) shown in the solute column of Comparative Example 1 was mixed with one of solvents 1 to 2 to prepare each mixture (two types of mixtures with different solvents). The same procedure was followed for Comparative Examples 2 to 5. When solvent 1 or 2 was used, the concentration of the solute in the mixture was 1% by mass. When using solvent 2, triethylamine was further used as a base, and the solute, solvent 2, and triethylamine were mixed to obtain the mixture. The amount of triethylamine used was 1% by mass of the total amount of the mixture. 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.

[0067] [evaluation] <Preparation of evaluation test specimens> As described above, glass plates were immersed in each prepared mixture for 1 minute. After removing the glass plates from the mixture, if the mixture contained solvents 1 and 2, the glass plates were dried at room temperature (25°C) for 20 minutes to obtain evaluation test specimens.

[0068] <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 Table 1.

[0069] <Evaluation Criteria for Oil Repellency> In this invention, regardless of the solvent 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 superior oil repellency. If the solute did not dissolve in the solvent, this result was indicated as "slowly soluble" in Table 1. The contact angle was not measured when the solute did not dissolve in the solvent. Furthermore, if the contact angle was not measured, it was indicated as "-" in Table 1.

[0070] [Table 1]

[0071] The details of each component shown in Table 1 are as follows: (solvent) • Solvent 1 (IPA): Isopropanol When solvent 1 was used, the concentration of the solute in the mixture was 1% by mass. No base was used when solvent 1 was employed. • Solvent 2 (AE-3000): Product name Asahi Clean AE-3000 (manufactured by AGC Corporation). CF2HCF2OCH2CF3. As described above, when solvent 2 was used, triethylamine was further used as a base, and the solute, solvent 2, and triethylamine were mixed to obtain the mixture. The amount of triethylamine used was 1% by mass of the total amount of the mixture. The concentration of the solute in the mixture when solvent 2 was used was 1% by mass.

[0072] (solute) • Formula (X1): The compound represented by the above formula (X1) produced in Example 1. Formula (Y1): 4-(trifluoromethoxy)aniline (structure shown below), manufactured by Tokyo Chemical Industry Co., Ltd. [ka]

[0073] 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]

[0074] The results in Table 1 confirm that the phosphate compounds and salts of the present invention exhibit the desired effects. On the other hand, compounds lacking a phosphate group exhibited insufficient oil repellency (Comparative Examples 1 and 2). Furthermore, compounds lacking both a trifluoromethoxy group and a phosphate group also exhibited insufficient oil repellency (Comparative Examples 3 to 5).

Claims

1. A phosphate compound represented by the following formula (X). 【Chemistry 1】 In formula (X), Q １ Each of these independently represents a single bond or a divalent organic group. Q ２ Each of these independently represents a (p+1) valence linking group. n represents 1 to 2, p represents 1 to 3, m represents 1 through 5.

2. A salt of the phosphate compound according to claim 1.

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