Fluorinated compound, fluoropolymer and surface treatment agent prepared using the same

Abstract

To provide a novel fluorinated compound having a trifluoromethoxy group and capable of forming a polymer with excellent oil repellency.SOLUTION: Provided are: a fluorinated compound represented by the formula; a fluoropolymer having constituent units formed from the fluorinated compound; and a surface treatment agent comprising the fluoropolymer and a solvent. In the formula, X is an oxygen atom, a sulfur atom, or a linking group represented by a specific formula; R1 is a phenyl group in which at least one hydrogen atom has been replaced with a trifluoromethoxy group, and R2, R3, and R4 are each independently a hydrogen atom or a C1-C4 alkyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fluorine-containing compound, a fluorine-containing polymer, and a surface treatment agent using the same. [Background technology]

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

[0003] [Patent Document 1] Patent No. 6670615 Summary of the Invention [Problem to be solved by the invention]

[0004] It is known that compounds containing perfluoroalkyl groups generate perfluorocarboxylic acids and the like during the decomposition process. Among perfluorocarboxylic acids, perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are known to be highly chemically stable but difficult to decompose in the environment and to have a high tendency to accumulate in living organisms and the environment. As a result, various scientific discussions have been held internationally regarding target values ​​and standards for these substances, and they are becoming regulated substances in various countries. On the other hand, it has been confirmed that PFHxA (perfluorohexanoic acid) and perfluorocarboxylic acids with even shorter carbon chains have much lower biotoxicity and bioaccumulation potential than PFOS and PFOA, so perfluoroalkyl group-containing compounds whose decomposition products become PFHxA or perfluorocarboxylic acids with even shorter carbon chains are widely used as alternative technologies. However, even with these alternative compounds, the decomposition product, perfluorocarboxylic acid, remains chemically stable, and there remains concern that if it continues to be released into the environment, it will accumulate in the environment over a long period of time and cause harm to the human body and the environment. Therefore, there is a demand for new alternative compounds. On the other hand, it is known that compounds containing trifluoromethoxy groups easily decompose in the environment (for example, in environments above -20°C) because CF3OH, which is expected to be generated during the decomposition process, is a very unstable compound.

[0005] Therefore, an object of the present invention is to provide a novel fluorine-containing compound which has a trifluoromethoxy group and can form a polymer having excellent oil repellency. Another object of the present invention is to provide a fluorine-containing polymer and a surface treatment agent. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0007] [1] A fluorine-containing compound represented by the following formula (M): [ka] In formula (M), X is an oxygen atom, a sulfur atom, or a linking group represented by formula (A) described later, R1 is a phenyl group in which at least one hydrogen atom is substituted with a trifluoromethoxy group, and R2, R3, and R4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. [2] The fluorine-containing compound according to [1], wherein in R1, the trifluoromethoxy group is bonded to at least the p-position of the phenyl group. [3] A fluorine-containing polymer having a structural unit formed from the fluorine-containing compound according to [1] or [2]. [4] A surface treatment agent comprising the fluorine-containing polymer according to [3] and a solvent. Effect of the Invention

[0008] According to the present invention, there can be provided a novel fluorine-containing compound which has a trifluoromethoxy group and can form a polymer having excellent oil repellency. The present invention can also provide a fluorine-containing polymer and a surface treatment agent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention will be described in detail below. The following description of the configuration may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "~" means a range including the numerical values ​​written before and after "~". In the present specification, each component may be used alone or in combination of two or more kinds. In this specification, when two or more types of a component are used in combination, the "content" of the component means the total content of those two or more types, unless otherwise specified. In the present specification, the method for producing each component is not particularly limited unless otherwise specified. For example, a conventionally known method may be used. In this specification, (meth)acrylic acid refers to acrylic acid or methacrylic acid. In this specification, with regard to the polymer obtained from the fluorine-containing compound of the present invention, the fluorine-containing polymer of the present invention, or the surface treatment agent of the present invention, better oil repellency is also referred to as "the effect of the present invention is better."

[0010] [Fluorine-containing compound of the present invention] The fluorine-containing compound of the present invention will now be described. The fluorine-containing compound of the present invention is a fluorine-containing compound represented by the following formula (M). [ka] In formula (M), X is an oxygen atom, a sulfur atom, or a linking group represented by formula (A) described later, R1 is a phenyl group in which at least one hydrogen atom is substituted with a trifluoromethoxy group, and R2, R3, and R4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0011] Even if the fluorine-containing compound of the present invention or the fluorine-containing polymer of the present invention is unexpectedly released into the environment, CF3OH, which may be generated from the trifluoromethoxy group by decomposition, is an unstable compound and easily decomposes in the environment (for example, in an environment above -20°C), so that the risk of remaining in the environment and traveling long distances can be significantly reduced. It is considered that the fluorine-containing polymer of the present invention can reduce the environmental load.

[0012] [X] In the present invention, in formula (M), X is an oxygen atom, a sulfur atom, or a linking group represented by the following formula (A). From the viewpoints of achieving superior effects of the present invention and not impairing water repellency, X is preferably a linking group represented by the following formula (A). The linking group represented by formula (A) is as follows. [ka]

[0013] ·n In formula (A), n is an integer of 0 to 8. From the viewpoints of achieving superior effects of the present invention and not impairing water repellency, n is preferably 0 or 1, and more preferably 0.

[0014] ·R In formula (A), R is a linear or branched alkylene group having 1 to 4 carbon atoms, or a phenylene group. Examples of the linear or branched alkylene group having 1 to 4 carbon atoms include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group; and branched alkylene groups such as an isopropylene group and an isobutylene group. When the above n is 1 or more, from the viewpoints of achieving a superior effect of the present invention and not impairing water repellency, R is preferably a linear alkyl group having 2 to 4 carbon atoms or a phenylene group, and more preferably a phenylene group.

[0015] Q1 In formula (A), Q1 is an oxygen atom or NH.

[0016] Y In formula (A), Y is any one of the linking groups represented by the following formulas (y1) to (y4). When the linking groups represented by the formulas (y1) to (y4) are incorporated into Y in the formula (A), the formulas (y1) to (y4) can be incorporated into Y in the formula (A) in the state described below or by inverting them left and right. However, a preferred embodiment includes the linking groups represented by the formulas (y1) to (y4) being incorporated into Y in the formula (A) in the state described below. [ka]

[0017] R5, R6 In the formulas (y2) to (y4), R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group represented by the following formula (B).

[0018] Alkyl groups with 1 to 4 carbon atoms Examples of the alkyl group having 1 to 4 carbon atoms as R5 and R6 include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0019] A group represented by formula (B) The group represented by formula (B) is as follows. [ka]

[0020] In formula (B), m is an integer of 0 to 8.

[0021] In formula (B), Ra is a linear or branched alkylene group or a phenylene group having 1 to 4 carbon atoms. Examples of the linear or branched alkylene group having 1 to 4 carbon atoms as Ra include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group; and branched alkylene groups such as an isopropylene group and an isobutylene group.

[0022] In formula (A), Q2 is an oxygen atom or NH.

[0023] In formula (B), Rb, Rc, and Rd each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms represented by Rb, Rc, and Rd include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0024] In formula (B), Z is a linking group represented by the following formula (z1) or (z2). The linking group represented by formula (z1) or (z2) may be incorporated into Z in formula (B) in the state described below. [ka]

[0025] In formula (z2), Re is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms represented by Re include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0026] R7, R8 In the formulae (y2) to (y4), R7 and R8 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms as R7 and R8 include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0027] Preferred embodiment of Y From the viewpoint of achieving better effects of the present invention, Y is preferably any one of the linking groups represented by formula (y1) to (y2), and more preferably a linking group represented by formula (y1) or a linking group represented by formula (y2) in which R5 is a hydrogen atom.

[0028] [R1] In the present invention, in formula (M), R1 is a phenyl group in which at least one hydrogen atom is substituted with a trifluoromethoxy group. R1 may be a phenyl group in which at least one of the five hydrogen atoms is substituted with a trifluoromethoxy group. Two or more hydrogen atoms in the phenyl group may be substituted with trifluoromethoxy groups. In order for R1 to exhibit the effects of the present invention, at least one hydrogen atom of the phenyl group must be substituted with a trifluoromethoxy group.

[0029] The trifluoromethoxy group may be bonded to any of the o-, m- or p-positions of the phenyl group.

[0030] In terms of obtaining superior effects of the present invention, it is preferable that the trifluoromethoxy group be bonded to the p-position of the phenyl group in R1.

[0031] [R2, R3, R4] In the present invention, in formula (M), R2, R3, and R4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms as R2, R3, and R4 include a methyl group, an ethyl group, a propyl group, and a butyl group. From the viewpoint of obtaining a more excellent effect of the present invention, the combination of R2, R3, and R4 is preferably an embodiment in which R2, R3, and R4 are all hydrogen atoms, or an embodiment in which R2 is a methyl group and R3 and R4 are all hydrogen atoms. The most preferred embodiment is an embodiment in which R2, R3, and R4 are all hydrogen atoms.

[0032] Preferred embodiment of fluorine-containing compound From the viewpoint of obtaining superior effects of the present invention, specific examples of more preferred structures of the fluorine-containing compound of the present invention are shown below. [ka] JPEG2025050338000008.jpg89146

[0033] Synthesis of fluorine-containing compounds Examples of a method for synthesizing the fluorine-containing compound of the present invention include the following synthesis methods 1 and 2. ·Synthesis method 1 When the fluorine-containing compound of the present invention has the formula (y1) or (y2) as Y in the formula (M), the corresponding synthesis method 1 can be, for example, a method of reacting trifluoromethoxyphenol, trifluoromethoxyaniline or a precursor represented by the following formula (pre1) with (meth)acrylic acid chloride in a solvent (e.g., dichloromethane, methylene chloride) in the presence of a catalyst (e.g., triethylamine, triethylenediamine). After the reaction, purification can be carried out as appropriate. [ka] In formula (pre1), x1 is an oxygen atom or NH.

[0034] ·Synthesis method 2 When the fluorine-containing compound of the present invention has the formula (y3) or (y4) as Y in the formula (M), the corresponding synthesis method 2 can be, for example, a method of reacting trifluoromethoxyphenol or trifluoromethoxyaniline with a (meth)acrylic acid ester having an isocyanate group, such as (meth)acrylic acid-2-isocyanatoethyl, in a solvent (e.g., tetrahydrofuran). In the above reaction, a catalyst (e.g., N,N-diisopropylethylamine, triethylamine, triethylenediamine) may be used. After the reaction, appropriate purification can be performed.

[0035] ·Applications The fluorine-containing compound of the present invention can be used, for example, as a monomer for producing a polymer.

[0036] [Fluorine-containing polymer of the present invention] The fluorine-containing polymer of the present invention is a fluorine-containing polymer having structural units formed from the fluorine-containing compound of the present invention. The constituent units contained in the fluorine-containing polymer of the present invention are not particularly limited as long as they contain a constituent unit formed by the fluorine-containing compound of the present invention. The structural unit formed by the fluorine-containing compound of the present invention has a structure in which the double bond in the above formula (M) is cleaved. The structural unit formed by the fluorine-containing compound of the present invention has a phenyl group derived from R1 in the above formula (M) in which at least one hydrogen atom is substituted with a trifluoromethoxy group. The fluorine-containing polymer of the present invention may have the structural unit formed by the fluorine-containing compound of the present invention either alone or in combination of two or more kinds. The structural units of the fluorine-containing polymer of the present invention may further have structural units (other structural units) other than the structural units formed by the fluorine-containing compound of the present invention. The other structural units are not particularly limited as long as they are structural units formed by monomers copolymerizable with the fluorine-containing compound of the present invention. From the viewpoint of reducing the burden on the environment, the fluorine-containing polymer of the present invention desirably does not contain any structural units containing perfluoroalkyl groups other than trifluoromethoxy groups. Furthermore, from the viewpoint of maintaining oil repellency, the structural units formed by the fluorine-containing compound of the present invention desirably account for 50 mass% or more and 100 mass% or less of all structural units possessed by the fluorine-containing polymer of the present invention, more preferably 80 mass% or more, and even more preferably 90 mass% or more.

[0037] Weight average molecular weight of the fluorine-containing polymer of the present invention The weight-average molecular weight of the fluoropolymer of the present invention is not particularly limited, but the lower limit of the weight-average molecular weight is preferably 10,000 or more from the viewpoint of oil resistance and water resistance, and the upper limit of the weight-average molecular weight is preferably 1,000,000 or less from the viewpoint of solubility in solvents.

[0038] Method for producing the fluorine-containing polymer of the present invention The method for producing the fluorine-containing polymer of the present invention is not particularly limited. As an example of the method for producing the fluorine-containing polymer of the present invention, for example, the fluorine-containing polymer of the present invention can be produced by polymerizing the fluorine-containing compound of the present invention in a solvent (e.g., ethyl acetate) in the presence of a polymerization initiator (e.g., dimethyl 2,2'-azobis(2-methylpropionate)) under conditions of 60 to 80°C. In addition, during polymerization, a monomer copolymerizable with the fluorine-containing compound of the present invention may be further used as necessary.

[0039] Uses of the fluorine-containing polymer of the present invention The fluoropolymer of the present invention can be used, for example, in a surface treatment agent.

[0040] [Surface treatment agent of the present invention] The surface treatment agent of the present invention is a surface treatment agent which contains the fluoropolymer of the present invention and a solvent.

[0041] [Fluorine-containing polymer] The fluorine-containing polymer contained in the surface treatment agent of the present invention is not particularly limited as long as it is the fluorine-containing polymer of the present invention.

[0042] [solvent] The solvent contained in the surface treatment agent of the present invention is not particularly limited as long as it can disperse and / or dissolve the fluorine-containing polymer of the present invention. Examples of the solvent include fluorine-based solvents; hydrocarbon organic solvents; esters such as ethyl acetate and butyl acetate; and ketones such as acetone and methyl ethyl ketone.

[0043] Examples of the fluorine-based solvent include hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs). Specific examples of the fluorine-based solvent are shown below, but the fluorine-based solvent is not limited thereto.

[0044] m-Xylene hexafluoride p-Xylene hexafluoride CF3CH2CF2CH3 CF3CH2CF2H C6F 13 OCH3 C6F 13 OC2H5 C6F 13 CH2CH3 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 (In the above examples, the subscripts m and n each independently represent an integer from 1 to 20.) and mixtures thereof An example of the mixture is a mixture of CF3(CF2)3OC2H5 and (CF3)2CFCF2OC2H5, which are isomers of C4F9OCH2CH3 (ethyl nonafluorobutyl ether).

[0045] Examples of the hydrocarbon organic solvent 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.

[0046] Fluorine-containing polymer concentration The concentration of the fluoropolymer of the present invention contained in the surface treatment agent of the present invention is preferably from 0.1 to 10 mass %, more preferably from 1 to 5 mass %, of the total amount of the surface treatment agent of the present invention, from the viewpoint of fully exerting the effects of the present invention. Solvent content The content of the solvent is not particularly limited, but from the viewpoint of handleability as a surface treatment agent, it is preferably 80 mass % or more of the total amount of the surface treatment agent of the present invention.

[0047] Additives The surface treatment agent of the present invention may further contain, for example, a pH adjuster, a rust inhibitor, a dye, a flame retardant, an antifoaming agent, and an antistatic agent, if necessary, within the range that does not impair the effects of the present invention.

[0048] Method for producing the surface treatment agent of the present invention As a method for producing the surface treatment agent of the present invention, for example, the surface treatment agent of the present invention can be produced by mixing the fluoropolymer of the present invention, a solvent, and additives that can be contained as necessary.

[0049] (Application) An example of a method for using the surface treatment agent of the present invention is a method for applying the surface treatment agent of the present invention to a substrate. By applying the surface treatment agent, a layer of the surface treatment agent is formed on the surface of the substrate, and the oil repellency of the substrate surface can be improved. Furthermore, by applying the surface treatment agent, excellent water repellency can be further imparted to the surface of the substrate. The method for applying the surface treatment agent of the present invention to a substrate is not particularly limited, and examples thereof include coating. After the surface treatment agent of the present invention is applied to the substrate, the solvent can be dried, for example, under conditions of 10 to 120°C.

[0050] Examples of materials for the substrate include glass, plastic, rubber, metal, and ceramic. Specific examples of the above-mentioned substrates include molded products used around water, such as bathroom components, washbasin components, and kitchen components; daily necessities, such as umbrellas, shoes, and bags; exterior-related products for buildings, such as bridge piers, roofs, and exterior walls; interior-related products, such as floors and interior walls; home appliances and other housing products; vehicle bodies, such as ships, airplanes, and automobiles (including exterior and interior materials); and electronic circuit boards. EXAMPLES

[0051] The present invention will be described in more detail below with reference to the following examples, in which Examples 1 to 15 are working examples and Examples 16 to 19 are comparative examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. In the following, unless otherwise specified, "parts" and "%" refer to "parts by mass" and "% by mass". In this specification, the fluorine-containing compound produced in Example 1 may be referred to as Monomer 1, the fluorine-containing polymer produced using Monomer 1 may be referred to as Fluorine-containing Polymer 1, and the surface treatment agent containing Fluorine-containing Polymer 1 may be referred to as Surface Treatment Agent 1. The same applies to other examples. Regarding the compounds used as raw materials in the examples, unless otherwise specified, the above compounds were obtained from the market.

[0052] < 1 The H-NMR measurement is shown below. The substance to be measured (each monomer synthesized in the examples) was dissolved in deuterated solvent chloroform-d, and the concentration of the substance to be measured was adjusted to about 0.2 mass%. SiMe4 was used as a standard. The prepared solution was 1 The mixture was transferred to a 1 H-NMR tube. The measurement conditions are as follows. Equipment: JNM-ECZ400R / S1 (manufactured by JEOL Ltd.) Nuclide: Proton Accumulation count: 16

[0053] Example 1 Synthesis of Monomer 1 In a four-neck flask, 9.21 g (51.7 mmol) of 4-trifluoromethoxyphenol and 78 mL of dichloromethane were mixed and cooled in ice water. 7.85 g (77.5 mmol) of triethylamine was added dropwise, followed by 5.61 g (62.0 mmol) of acrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 11.25 g of the target product. [ka]

[0054] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):6.04(dd,1H,CH),6.32(dd,1H,CH),6.62(dd,1H,CH),7.17(m,2H,2CH),7.25(m,2H,2CH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0055] Example 2 Synthesis of Monomer 2 In a four-neck flask, 9.21 g (51.7 mmol) of 4-trifluoromethoxyphenol and 60 mL of dichloromethane were mixed and cooled in ice water. 7.85 g (77.5 mmol) of triethylamine was added dropwise, followed by 6.53 g (62.0 mmol) of methacrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 11.45 g of the target product. [ka]

[0056] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):2.06(m,3H,CH3),5.78(m,1H,CH),6.36(m,1H,CH),7.16(m,2H,2CH),7.24(m,2H,2CH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0057] Example 3 Synthesis of Monomer 3 In a four-neck flask, 8.05 g (45.4 mmol) of 4-trifluoromethoxyaniline and 80 mL of dichloromethane were mixed and cooled in ice water. 5.25 g (51.9 mmol) of triethylamine was added dropwise, followed by 3.92 g (43.3 mmol) of acrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 8.38 g of the target product. [ka]

[0058] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):5.78(dd,1H,CH),6.26(dd,1H,CH),6.44(dd,1H,CH),7.18(m,2H,2CH),7.63(m,3H,2CH,NH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0059] Example 4 Synthesis of Monomer 4 In a four-neck flask, 9.65 g (54.5 mmol) of 4-trifluoromethoxyaniline and 96 mL of dichloromethane were mixed and cooled in ice water. 5.78 g (57.1 mmol) of triethylamine was added dropwise, followed by 5.43 g (51.9 mmol) of methacrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 11.50 g of the target product. [ka]

[0060] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):2.06(m,3H,CH3),5.49(m,1H,CH),5.80(m,1H,CH),7.19(m,2H,2CH),7.59(m,3H,2CH,NH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0061] Example 5 Synthesis of Monomer 5 In a four-neck flask, 11.51 g (64.6 mmol) of 3-trifluoromethoxyphenol and 90 mL of dichloromethane were mixed and cooled in ice water. 9.81 g (96.9 mmol) of triethylamine was added dropwise, followed by 7.02 g (77.5 mmol) of acrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 14.67 g of the target product. [ka]

[0062] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):6.05(dd,1H,CH),6.32(dd,1H,CH),6.63(dd,1H,CH),7.06(m,1H,CH),7.12(m,2H,2CH),7.41(t,1H,CH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0063] Example 6 Synthesis of Monomer 6 In a four-neck flask, 10.85 g (60.9 mmol) of 3-trifluoromethoxyphenol and 90 mL of dichloromethane were mixed and cooled in ice water. 9.25 g (91.4 mmol) of triethylamine was added dropwise, followed by 8.60 g (82.3 mmol) of methacrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5 mass%) and water, and the solvent was distilled off under reduced pressure to obtain 13.71 g of the target product. [ka]

[0064] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):2.05(m,3H,CH3),5.78(m,1H,CH),6.35(m,1H,CH),7.04(m,1H,CH),7.10(m,2H,2CH),7.40(t,1H,CH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0065] Example 7 Synthesis of Monomer 7 In a four-neck flask, 9.65 g (54.5 mmol) of 3-trifluoromethoxyaniline and 96 mL of dichloromethane were mixed and cooled in ice water. 7.88 g (77.9 mmol) of triethylamine was added dropwise, followed by 4.70 g (51.9 mmol) of acrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 11.44 g of the target product. [ka]

[0066] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):5.80(dd,1H,CH),6.25(dd,1H,CH),6.45(dd,1H,CH),6.98(dd,1H,CH),7.33(t,1H,CH),7.44(d,1H,CH),7.57(brs,1H,NH),7.64(s,1H,CH) the above 1From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0067] Example 8 Synthesis of Monomer 8 In a four-neck flask, 9.86 g (55.7 mmol) of 3-trifluoromethoxyaniline and 104 mL of dichloromethane were mixed and cooled in ice water. 8.05 g (79.5 mmol) of triethylamine was added dropwise, followed by 7.20 g (68.8 mmol) of methacrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 13.85 g of the target product. [ka]

[0068] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):2.06(m,3H,CH3),5.50(m,1H,CH),5.80(m,1H,CH),6.98(m,1H,CH),7.33(t,1H,CH),7.42(m,1H,CH),7.62(m,2H,CH,NH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0069] Example 9 Synthesis of Monomer 9 In a four-neck flask, 11.51 g (64.6 mmol) of 2-trifluoromethoxyphenol and 120 mL of dichloromethane were mixed and cooled in ice water. 9.81 g (96.9 mmol) of triethylamine was added dropwise, followed by 8.18 g (90.3 mmol) of acrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 14.04 g of the target product. [ka]

[0070] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):6.07(dd,1H,CH),6.34(dd,1H,CH),6.65(dd,1H,CH),7.31(m,4H,4CH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0071] Example 10 Synthesis of Monomer 10 In a four-neck flask, 10.85 g (60.9 mmol) of 2-trifluoromethoxyphenol and 90 mL of dichloromethane were mixed and cooled in ice water. 9.25 g (91.4 mmol) of triethylamine was added dropwise, followed by 8.92 g (85.4 mmol) of methacrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 14.85 g of the target product. [ka]

[0072] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):2.07(m,3H,CH3),5.80(m,1H,CH),6.38(m,1H,CH),7.30(m,4H,4CH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0073] Example 11 Synthesis of Monomer 11 In a four-neck flask, 12.07 g (68.1 mmol) of 2-trifluoromethoxyaniline and 120 mL of dichloromethane were mixed and cooled in ice water. 9.85 g (97.3 mmol) of triethylamine was added dropwise, followed by 7.04 g (77.8 mmol) of acrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 13.70 g of the target product. [ka]

[0074] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):5.83(dd,1H,CH),6.29(dd,1H,CH),6.45(dd,1H,CH),7.12(m,1H,CH),7.28(m,2H,2CH),7.54(brs,1H,NH),8.50(d,1H,CH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0075] Example 12 Synthesis of Monomer 12 In a four-neck flask, 12.73 g (71.9 mmol) of 2-trifluoromethoxyaniline and 120 mL of dichloromethane were mixed and cooled in ice water. 10.80 g (106.7 mmol) of triethylamine was added dropwise, followed by 10.57 g (101.1 mmol) of methacrylic acid chloride, and the temperature was raised to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the aqueous layer and organic layer were separated. The obtained organic layer was washed with an aqueous sodium hydrogen carbonate solution (2.5% by mass) and water, and the solvent was distilled off under reduced pressure to obtain 13.74 g of the target product. [ka]

[0076] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):2.09(m,3H,CH3),5.53(m,1H,CH),5.87(m,1H,CH),7.13(m,1H,CH),7.30(m,2H,2CH),7.90(brs,1H,NH),8.49(dd,1H,CH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0077] Example 13 Synthesis of Monomer 13 In a four-neck flask, 10.00 g (56.2 mmol) of 4-trifluoromethoxyphenol and 56 mL of tetrahydrofuran were mixed, and 0.36 g (2.81 mmol) of N,N-diisopropylethylamine and 8.72 g (61.8 mmol) of 2-isocyanatoethyl acrylate were added, and the mixture was heated under reflux for 21 hours. The target product was then separated by column chromatography (hexane / acetone), and the solvent was distilled off under reduced pressure to obtain 16.10 g of the target product. The yield of the target product was 89.8%. [ka]

[0078] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):3.58(m,2H,CH2),4.31(m,2H,CH2),5.38(brs,1H,NH),5.89(dd,1H,CH),6.15(dd,1H,CH),6.46(dd,1H,CH),7.17(m,4H,4CH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0079] Example 14 Synthesis of Monomer 14 In a four-neck flask, 8.00 g (45.2 mmol) of 4-trifluoromethoxyaniline and 45 mL of tetrahydrofuran were mixed, and 7.01 g (49.68 mmol) of 2-isocyanatoethyl acrylate was added, and the mixture was heated under reflux for 14 hours. The target product was then separated by column chromatography (hexane / ethyl acetate), and the solvent was distilled off under reduced pressure to obtain 10.80 g of the target product. The yield of the target product was 74.9%. [ka]

[0080] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):3.51(t,2H,CH2),4.24(t,2H,CH2),5.81(m,2H,CH,NH),6.08(dd,1H,CH),6.39(dd,1H,CH),7.07(m,2H,2CH),7.26(m,2H,2CH),7.53(m,1H,NH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0081] Example 15 Synthesis of precursor 15-1 First, 5.56 g (30.9 mmol) of 4-acetoxybenzoic acid and 56 mL of tetrahydrofuran were mixed in a four-neck flask, and 4.01 g (33.7 mmol) of thionyl chloride was added dropwise, followed by heating to reflux. After confirming the disappearance of the raw materials by GC, the mixture was concentrated under reduced pressure, and 56 mL of tetrahydrofuran, 3.99 g (30.9 mmol) of diisopropylethylamine, and 5.00 g (28.1 mmol) of 4-trifluoromethoxyphenol were added and stirred overnight. After confirming the disappearance of the raw materials by GC (gas chromatography), water was added to stop the reaction, and after extraction with ethyl acetate, the organic layer was dried over magnesium sulfate. The obtained organic layer was separated by silica gel column chromatography (hexane / ethyl acetate) and concentrated under reduced pressure. The obtained crystals were recrystallized using methylene chloride and hexane, and the crystals were dried under reduced pressure to obtain 4.12 g of precursor 15-1. The reaction formula for obtaining precursor 15-1 is as follows. [ka]

[0082] Synthesis of precursor 15-2 Next, in a four-neck flask, 4.12 g (12.1 mmol) of precursor 15-1 synthesized as described above was dissolved in a mixed solvent of 24 mL of tetrahydrofuran and 24 mL of methanol, and a 1:1 mixed solution of an aqueous ammonium chloride solution (1 M) and an aqueous sodium hydroxide solution (1 M) was added dropwise. After confirming the disappearance of the raw materials by TLC, the solution was neutralized with hydrochloric acid (1 M) and extracted with methylene chloride. The obtained organic layer was concentrated under reduced pressure to obtain 3.72 g of a white solid of precursor 15-2. The reaction formula for obtaining precursor 15-2 is as follows. [ka]

[0083] Synthesis of Monomer 15 In a four-neck flask, 3.72 g (12.5 mmol) of the precursor 15-2 synthesized as described above was dissolved in 25 mL of methylene chloride, and 1.77 g (13.7 mmol) of diisopropylethylamine was added dropwise. Then, 1.24 g (13.7 mmol) of acrylic acid chloride was added and stirred at room temperature for 2 hours. After confirming the disappearance of the raw material by GC, water was added to stop the reaction, and after extraction with methylene chloride, the organic layer was dried with magnesium sulfate. The obtained organic layer was separated by silica gel column chromatography (hexane / methylene chloride) and concentrated under reduced pressure. The obtained crystals were washed with hexane and dried under reduced pressure to obtain 2.48 g of the target product. [ka]

[0084] The compound obtained by the above reaction 1 The H-NMR chemical shifts were as follows: δ (ppm):6.08(d,1H,CH),6.35(dd,1H,CH),6.66(d,1H,CH),7.28(m,6H,6CH),8.25(m,2H,2CH) the above 1 From the results of H-NMR, it was confirmed that the compound obtained by the above reaction had the structure of the reaction product shown in the above reaction formula.

[0085] [Production of fluorine-containing polymer] Production of fluorine-containing polymer 1 Monomer 1 (100 parts) synthesized in Example 1 as described above, ethyl acetate (300 parts), and V-601 (1 part; dimethyl 2,2'-azobis(2-methylpropionate); manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a reaction vessel, which was then replaced with nitrogen and sealed. A polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing fluorine-containing polymer 1, which is a polymer of monomer 1. The reaction formula for the above polymerization reaction is as follows: After 18 hours, a portion of the reaction solution was taken and analyzed by gas chromatography to confirm that the peak derived from Monomer 1 had completely disappeared, which indicated that the polymerization reaction had progressed quantitatively. The above reaction rate confirmation was used in the other examples as well. [ka]

[0086] Production of fluorine-containing polymers 2, 4-11, 13-14 A fluoropolymer 2 was produced by carrying out polymerization in the same manner as in the production of the above-mentioned fluoropolymer 1, except that 100 parts of Monomer 1 was changed to 100 parts of Monomer 2. The same applies to the fluorine-containing polymers 4 to 11 and 13 to 14.

[0087] Production of fluorine-containing polymer 3 Monomer 3 (100 parts) synthesized in Example 3 as described above, ethyl acetate (700 parts), and V-601 (1 part, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a reaction vessel, and the vessel was replaced with nitrogen and then sealed. A polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing a fluorine-containing polymer 3. The reaction formula of the above polymerization reaction is as follows. [ka]

[0088] Production of fluorine-containing polymer 12 Monomer 12 (100 parts) synthesized in Example 12 as described above, ethyl acetate (400 parts), and V-601 (1 part, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a reaction vessel, and the vessel was replaced with nitrogen and then sealed. A polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing a fluorine-containing polymer 12. The reaction formula of the above polymerization reaction is as follows. [ka]

[0089] -Production of fluorine-containing polymer 15 Monomer 15 (100 parts) synthesized in Example 15 as described above, ethyl acetate (500 parts), and V-601 (1 part, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a reaction vessel, and the vessel was replaced with nitrogen and then sealed. A polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing fluorine-containing polymer 15. The reaction formula of the above polymerization reaction is as follows. [ka]

[0090] Comparative Example 1 Phenyl acrylate (100 parts) as a monomer, ethyl acetate (300 parts), and V-601 (1 part, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a reaction vessel, and the vessel was replaced with nitrogen and then sealed. A polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing polyphenyl acrylate. The reaction formula of the above polymerization reaction is as follows. [ka]

[0091] Comparative Example 2 Polymerization was carried out in the same manner as in Comparative Example 1 above, except that 100 parts of phenyl acrylate was changed to 100 parts of phenyl methacrylate, to obtain an ethyl acetate solution containing polyphenyl methacrylate.

[0092] Comparative Example 3 N-phenylacrylamide (100 parts) as a monomer, ethyl acetate (700 parts), and V-601 (1 part, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a reaction vessel, and the vessel was replaced with nitrogen and then sealed. A polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing poly N-phenylacrylamide. The reaction formula of the above polymerization reaction is as follows. [ka]

[0093] Comparative Example 4 Polymerization was carried out in the same manner as in Comparative Example 1 above, except that 100 parts of phenyl acrylate was changed to 100 parts of N-phenyl methacrylamide, to obtain an ethyl acetate solution containing poly(N-phenyl methacrylamide).

[0094] [Manufacturing of surface treatment agents] Ethyl acetate was added to each of the solutions containing the polymer obtained as described above to produce a surface treatment agent containing the polymer and a solvent. In each of the surface treatment agents, the solid content of the polymer in the surface treatment agent was 2 mass%.

[0095] [evaluation] <Preparation of evaluation test pieces> A glass plate was immersed in each of the surface treatment agents prepared as described above for 1 minute, and then removed from the surface treatment agent and dried in a dryer at 120° C. for 5 minutes to obtain an evaluation specimen.

[0096] <Contact angle measurement> Water or n-hexadecane (n-HD) was dropped onto the evaluation test piece obtained as described above, and the contact angle (unit: degree) of water or n-hexadecane (n-HD) was measured using a contact angle meter DMo-501 (manufactured by Kyowa Interface Science Co., Ltd.) The contact angle was measured at five points for water or n-hexadecane, and the average was used as the evaluation value. The evaluation results are shown in Table 1 together with the structural formula of each monomer.

[0097] <Evaluation criteria for oil repellency> In the present invention, when the contact angle with n-hexadecane is 30 degrees or more, it is considered that the oil repellency is excellent. The larger the contact angle is, the more excellent the oil repellency is. From the viewpoint of superior oil repellency, the contact angle is preferably 40 degrees or more. On the other hand, when the contact angle was less than 30 degrees, the oil repellency was evaluated as poor.

[0098] (Evaluation criteria for water repellency) In this specification, a contact angle of water of 80 degrees or more is deemed to be excellent in water repellency. The larger the contact angle is, the more excellent the water repellency is. From the viewpoint of achieving superior water repellency, the contact angle is preferably 100 degrees or more. On the other hand, when the contact angle was less than 80 degrees, the water repellency was evaluated as being poor.

[0099] [Table 1]

[0100] [Table 2]

[0101] From the results in Table 1, it was confirmed that the fluorine-containing polymer of the present invention having structural units formed from the fluorine-containing compound of the present invention and the surface treatment agent of the present invention exhibit the desired effects (Examples 1 to 15).

[0102] On the other hand, the polymers and surface treatment agents having structural units formed from compounds not having a trifluoromethoxy group had poor oil repellency (Examples 16 to 19).

Claims

1. A fluorine-containing compound represented by the following formula (M): 【Chemistry 1】 In formula (M), X is an oxygen atom, a sulfur atom, or a linking group represented by the following formula (A), R １ is a phenyl group in which at least one hydrogen atom is substituted with a trifluoromethoxy group, R ２ , R ３ , R ４ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 【Chemistry 2】 In formula (A), n is an integer from 0 to 8; Q １ is an oxygen atom or NH, R is a linear or branched alkylene group having 1 to 4 carbon atoms or a phenylene group, and Y is any one of the linking groups represented by the following formulas (y1) to (y4): 【Chemistry 3】 In formulas (y2) to (y4), R ５ , R ６ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group represented by the following formula (B), ７ , R ８ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 【Chemistry 4】 In formula (B), m is an integer from 0 to 8; ２ represents an oxygen atom or NH; Ra represents a linear or branched alkylene group having 1 to 4 carbon atoms or a phenylene group; Rb, Rc, and Rd each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and Z represents a linking group represented by the following formula (z1) or (z2): 【Chemistry 5】 In formula (z2), Re is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

2. The R １ The fluorine-containing compound according to claim 1 , wherein the trifluoromethoxy group is bonded to the p-position of the phenyl group.

3. A fluorine-containing polymer having structural units formed from the fluorine-containing compound according to claim 1 or 2.

4. A surface treatment agent comprising the fluorine-containing polymer according to claim 3 and a solvent.

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