Fluorinated compound and fluoropolymer as well as surface treatment agents in which this is used

Abstract

A fluorine-containing compound represented by the following formula; a fluorine-containing polymer with a structural unit formed by the fluorine-containing compound; and a surface treatment agent comprising the fluorine-containing polymer and a solvent. In the formula, X is an oxygen atom, a sulfur atom, or a linkage group represented by the formula (A) below; R1 is a phenyl group in which at least one hydrogen atom is substituted with a trifluoromethoxy group; and each of R2, R3, and R4 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms.

Description

TECHNICAL AREA

[0001] The present invention relates to a fluorine-containing compound, a fluorine-containing polymer and a surface treatment agent in which this is used.

[0002] Priority is claimed from Japanese patent application No. 2023-159062, which was filed on September 22, 2023, and the contents of which are incorporated herein by reference. STATE OF THE ART

[0003] Traditionally, compositions containing fluorine-containing polymers and solvents are known as water-resistant and moisture-resistant coating materials. Furthermore, it is known that the aforementioned fluorine-containing polymers can contain structural units formed from (meth)acrylic acid esters and the like, which have phenyl groups (see, for example, patent document 1). Document listPatent documents

[0004] Patent document 1: Japanese patent no. 6670615 SUMMARY OF THE INVENTION Technical Problem

[0005] It is known that compounds containing perfluoroalkyl groups produce perfluorocarboxylic acids and the like during the decomposition process.

[0006] Regarding perfluorocarboxylic acids and the like, various international scientific discussions have taken place concerning target values ​​and standards for them, and they are becoming substances that are subject to restrictions in various countries, since perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are chemically very stable, but resist degradation in the environment and are also known to have a high potential for bioaccumulation and environmental accumulation.

[0007] On the other hand, since it has been confirmed that perfluorohexanoic acid (PFHxA) and perfluorocarboxylic acids with even shorter carbon chains have a significantly lower biotoxicity and bioaccumulation potential compared to PFOS and PFOA, perfluoroalkyl group-containing compounds whose decomposition products are PFHxA or perfluorocarboxylic acids with even shorter carbon chains are widely used as alternative technologies.

[0008] Even with these alternative compounds, perfluorocarboxylic acid remains chemically stable as a decomposition product, and if continuously released into the environment, it could accumulate over a long period, remaining a problem in terms of its adverse effects on human health and the environment. Therefore, there is a need for new, alternative compounds.

[0009] Furthermore, it is known that compounds containing trifluoromethoxy groups decompose easily in the environment (for example, in an environment above -20 °C), since CF3OH, which is expected to be produced during the decomposition process, is a very unstable compound.

[0010] Accordingly, an object of the present invention is to provide a new fluorine-containing compound which has a trifluoromethoxy group and can form a polymer with excellent water and oil repulsion.

[0011] Another object of the present invention is the provision of a fluorine-containing polymer and a surface treatment agent. Solution to the problem

[0012] As a result of intensive investigations to solve the above problems, the inventors of the present invention have found that the problems can be solved by the following configuration.

[0013] [1] Fluorine-containing compound represented by the formula (M) below:

[0014] In formula (M), X is an oxygen atom, a sulfur atom, or a linkage group represented by formula (A) below; R1 is a phenyl group in which at least one hydrogen atom is substituted with a trifluoromethoxy group; and each of R2, R3, and R4 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms.

[0015] In formula (A) n is an integer from 0 to 8; Q1 is an oxygen atom or a divalent group represented by -NH-; R is an unbranched or branched alkylene group with 1 to 4 carbon atoms or a phenylene group; and Y is one of linking groups represented by the formulas (y1) to (y4) below.

[0016] In formulas (y2) to (y4), each of R5 and R6 independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a group represented by formula (B) below; and each of R7 and R8 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms.

[0017] In formula (B), m is an integer from 0 to 8; Q2 is an oxygen atom or a divalent group represented by -NH-; R a is an unbranched or branched alkylene group with 1 to 4 carbon atoms or a phenylene group; each of R b , R c and R d independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms; and Z is a linking group represented by the following formula (z1) or (z2).

[0018] In formula (z2) R ea hydrogen atom or an alkyl group with 1 to 4 carbon atoms.

[0019] [2] Fluorine-containing compound according to [1], wherein in the aforementioned R1 the aforementioned trifluoromethoxy group is bonded to a para-position of the aforementioned phenyl group.

[0020] [3] Fluorine-containing compound according to [1] or [2], wherein in the above-mentioned formula (M) X is a linking group represented by the above-mentioned formula (A).

[0021] [4] Fluorine-containing compound according to [3], wherein the Y mentioned above in the formula (A) above is a linking group represented by the formula (y1) or (y2) above.

[0022] [5] Fluorine-containing polymer having a structural unit formed by the fluorine-containing compound according to one of [1] to [4].

[0023] [6] Surface treatment agent comprising the fluorine-containing polymer according to [5] and a solvent. Advantageous effects of the invention

[0024] According to the present invention, a new fluorine-containing compound can be provided which has a trifluoromethoxy group and can form a polymer with excellent water and oil repulsion.

[0025] The present invention can also provide a fluorine-containing polymer and a surface treatment agent. DESCRIPTION OF EXECUTION FORMS

[0026] The present invention is described in detail below.

[0027] The explanation of the component elements described below may be based on representative embodiments of the present invention, however, the present invention is not limited to such embodiments.

[0028] In the present description, a numerical range specified using "to" represents a range that includes the numerical values ​​described before and after "to".

[0029] In the present description, each component can be used alone, or two or more types of them can be used in combination.

[0030] In the present description, if two or more types of a component are used in a combination, the "content" of that component refers to the total content of those two or more types, unless otherwise stated.

[0031] In this description, the manufacturing process for each component is not specifically limited unless otherwise stated. Examples include conventionally known processes.

[0032] In this description, (meth)acrylic acid refers to acrylic acid or methacrylic acid.

[0033] In the present description, 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, if its water repulsion and oil repulsion are further improved, shall also be referred to as "the effects of the present invention are further improved". [Fluorine-containing compound of the present invention]

[0034] The fluorine-containing compound of the present invention is described below.

[0035] The fluorine-containing compound of the present invention is a fluorine-containing compound represented by the following formula (M).

[0036] In formula (M), X represents an oxygen atom, a sulfur atom, or a linkage group represented by formula (A) described below; R1 represents a phenyl group in which at least one hydrogen atom is substituted with a trifluoromethoxy group; and each of R2, R3, and R4 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. R2 is preferably a hydrogen atom or a methyl group. R3 and R4 are preferably hydrogen atoms.

[0037] Even if the fluorine-containing compound or polymer of the present invention is unexpectedly released into the environment, the risk of it remaining in the environment and traveling long distances can be significantly reduced, since CF3OH, which can be generated from the trifluoromethoxy group upon decomposition, is an unstable compound and readily decomposes in the environment (for example, in an environment above -20 °C). It is therefore expected that the fluorine-containing polymer of the present invention and similar compounds can reduce environmental pollution.

[0038] In the present invention, X in formula (M) is an oxygen atom, a sulfur atom, or a linkage group represented by the following formula (A). With a view to further improving the effects of the present invention and to avoiding any impairment of water and oil repulsion, X is preferably a linkage group represented by the following formula (A).

[0039] The linking group represented by formula (A) is as follows.

[0040] In formula (A) n is an integer from 0 to 8. With a view to further improving the effects of the present invention and to avoiding any impairment of water and oil repulsion, n is preferably 0 or 1 and more preferably 0.

[0041] In formula (A), R is an unbranched or branched alkylene group with 1 to 4 carbon atoms or a phenylene group.

[0042] Examples of unbranched or branched alkylene groups with 1 to 4 carbon atoms include an unbranched alkylene group, such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group; and a branched alkylene group, such as an isopropylene group and an isobutylene group.

[0043] If the foregoing n is 1 or greater, R is preferably an unbranched alkylene group having 2 to 4 carbon atoms or a phenylene group, and more preferably a phenylene group, with a view to further improving the effects of the present invention and the absence of any impairment of water repulsion and oil repulsion.

[0044] In formula (A), Q1 is an oxygen atom or a divalent group represented by -NH-.

[0045] In formula (A), Y is one of the linking groups represented by the following formulas (y1) to (y4).

[0046] It should be noted that when the linking groups represented by formulas (y1) to (y4) are included in Y in formula (A), formulas (y1) to (y4) can be included in Y in formula (A) either in a state as described below or by flipping them left and right; however, it is preferred to include the linking groups represented by formulas (y1) to (y4) in Y in formula (A) in the state as described below.

[0047] In formulas (y2) to (y4), each of R5 and R6 independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a group represented by the following formula (B).

[0048] Examples of the aforementioned alkyl group with 1 to 4 carbon atoms, represented by R5 and R6, include a methyl group, an ethyl group, a propyl group and a butyl group.

[0049] The group represented by formula (B) is as follows.

[0050] In formula (B), m is an integer from 0 to 8.

[0051] In formula (B) R a An unbranched or branched alkylene group with 1 to 4 carbon atoms, or a phenylene group. Examples of the unbranched or branched alkylene group with 1 to 4 carbon atoms, represented by Ra, include an unbranched alkylene group, such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group; and a branched alkylene group, such as an isopropylene group and an isobutylene group.

[0052] In formula (B), Q2 is an oxygen atom or a divalent group represented by -NH-.

[0053] In formula (B), each of R represents b , R c and R d independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. Examples of the alkyl groups with 1 to 4 carbon atoms represented by R b , R c and R d The groups shown include a methyl group, an ethyl group, a propyl group and a butyl group.

[0054] In formula (B), Z is a combination group represented by the following formula (z1) or (z2). It should be noted that the combination group represented by formula (z1) or (z2) can be included in Z in formula (B) in a state described below.

[0055] In formula (z2) R ea hydrogen atom or an alkyl group with 1 to 4 carbon atoms. Examples of the alkyl group with 1 to 4 carbon atoms represented by R e The group shown comprises a methyl group, an ethyl group, a propyl group and a butyl group.

[0056] In formulas (y2) to (y4), each of R7 and R8 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. Examples of the alkyl groups with 1 to 4 carbon atoms represented by R7 and R8 include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0057] With a view to further improving the effects of the present invention, Y is preferably one of the linking groups represented by formulas (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.

[0058] In the present invention, R1 in formula (M) is a phenyl group in which at least one hydrogen atom is substituted with a trifluoromethoxy group.

[0059] For R1 to apply, it is sufficient that at least one of the five hydrogen atoms contained in a phenyl group is substituted with a trifluoromethoxy group. It is also possible that two or more hydrogen atoms in the aforementioned phenyl group are substituted by trifluoromethoxy groups.

[0060] In order to obtain the effects of the present invention, it is necessary for R1 that at least one hydrogen atom of the aforementioned phenyl group is substituted with a trifluoromethoxy group.

[0061] The trifluoromethoxy group can be bonded to one of the ortho (o-), meta (m-) and para (p-) positions of the preceding phenyl group.

[0062] With a view to further improving the effects of the present invention, it is preferred that the trifluoromethoxy group is bonded to the para-position of the preceding phenyl group in R1.

[0063] In the present invention, each of R2, R3, and R4 in formula (M) independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. Examples of the alkyl groups with 1 to 4 carbon atoms represented by R2, R3, and R4 include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0064] With a view to further improving the effects 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 hydrogen atoms. The most preferred embodiment is such that R2, R3, and R4 are all hydrogen atoms.

[0065] With a view to further improving the effects of the present invention, specific examples of more preferred structures of the fluorine-containing compound of the present invention are shown below.

[0066] Examples of methods for synthesizing the fluorine-containing compound of the present invention include the following synthesis methods 1 and 2. - Synthesis method 1

[0067] If the fluorine-containing compound of the present invention has formula (y1) or (y2) as Y in formula (M), examples of synthesis process 1 as the corresponding synthesis process include a process of reacting trifluoromethoxyphenol, trifluoromethoxyaniline, or a precursor represented by the following formula (Pre1), with (meth)acryloyl chloride in a solvent (for example, dichloromethane, methylene chloride) in the presence of a catalyst (for example, triethylamine, triethylenediamine). Purification may optionally be carried out after the reaction.

[0068] In formula (Vor1), x1 is an oxygen atom or a divalent group represented by -NH-. - Synthesis process 2

[0069] If the fluorine-containing compound of the present invention has formula (y3) or (y4) as Y in formula (M), examples of synthesis process 2, as the corresponding synthesis process, include a process of reacting trifluoromethoxyphenol or trifluoromethoxyaniline with a (meth)acrylic acid ester having an isocyanate group, such as 2-isocyanatoethyl(meth)acrylate, in a solvent (for example, tetrahydrofuran). A catalyst (for example, N,N-diisopropylethylamine, triethylamine, triethylenediamine) may be used in the above reaction. Purification may optionally be carried out after the reaction. - Applications

[0070] The fluorine-containing compound of the present invention can, for example, be used as a monomer for the production of a polymer. [Fluorine-containing polymer of the present invention]

[0071] The fluorine-containing polymer of the present invention is a fluorine-containing polymer with a structural unit formed from the fluorine-containing compound of the present invention.

[0072] The structural unit incorporated into the fluorine-containing polymer of the present invention is not specifically limited as long as it is a structural unit formed by the fluorine-containing compound of the present invention.

[0073] The structural unit formed by the fluorine-containing compound of the present invention has a structure in which the double bond in the preceding 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 preceding formula (M), in which at least one hydrogen atom is substituted with a trifluoromethoxy group.

[0074] The fluorine-containing polymer of the present invention can comprise structural units formed by the fluorine-containing compound of the present invention, either alone or in a combination of two or more types.

[0075] The structural unit incorporated into the fluorine-containing polymer of the present invention may further comprise a structural unit (additional structural unit) that is different from the structural unit formed by the fluorine-containing compound of the present invention. The additional structural unit is not specifically limited as long as it is a structural unit formed by a monomer that is copolymerizable with the fluorine-containing compound of the present invention.

[0076] With a view to reducing environmental pollution, the fluorine-containing polymer of the present invention preferably does not contain a structural unit containing a perfluoroalkyl group that is different from a trifluoromethoxy group.

[0077] Furthermore, the structural unit formed by the fluorine-containing compound of the present invention is preferably contained in an amount of 50 wt% or more and 100 wt% or less, more preferably 80 wt% or more and even more preferably 90 wt% or more, with a view to maintaining a water repulsion performance and oil repulsion performance relative to the total mass of all structural units contained in the fluorine-containing polymer of the present invention.

[0078] The average molecular weight of the fluorine-containing polymer of the present invention is not specifically limited; however, the lower limit of the average molecular weight with regard to oil and water resistance is preferably 10,000 or more, and the upper limit with regard to solvent solubility is preferably 1,000,000 or less. It should be noted that the average molecular weight is a weight average determined by gel permeation chromatography (GPC).

[0079] A process for preparing the fluorine-containing polymer of the present invention is not specifically limited. As an example of a process for preparing the fluorine-containing polymer of the present invention, the fluorine-containing polymer of the present invention can be prepared, for example, by polymerizing the fluorine-containing compound of the present invention in a solvent (for example, ethyl acetate) in the presence of a polymerization initiator (for example, dimethyl 2,2'-azobis(2-methylpropionate)) at a temperature of 60 to 80 °C. Furthermore, a monomer that is copolymerizable with the fluorine-containing compound of the present invention can optionally be used during the polymerization.

[0080] The fluorine-containing polymer of the present invention can, for example, be used in a surface treatment agent. [Surface treatment agents of the present invention]

[0081] The surface treatment agent of the present invention is a surface treatment agent comprising the fluorine-containing polymer of the present invention and a solvent. Since the surface treatment agent of the present invention exhibits excellent water and oil repellency, it can be used as a water and oil repellency composition and as a water and oil repellency agent.

[0082] The fluorine-containing polymer included in the surface treatment agent of the present invention is not specifically limited as long as it is the fluorine-containing polymer of the present invention.

[0083] The solvent contained in the surface treatment agent of the present invention is not specifically limited as long as it is able to disperse and / or dissolve the fluorine-containing polymer of the present invention.

[0084] Examples of solvents include a fluorine-based solvent, a hydrocarbon-based organic solvent, an ester (such as ethyl acetate and butyl acetate), and a ketone (such as acetone and methyl ethyl ketone).

[0085] Examples of fluorine-based solvents include hydrofluorocarbon (HFC) and hydrofluoroether (HFE).

[0086] Specific examples of the fluorine-based solvent include 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) mOCF2H, C8F 17 OCH3, C7F 15 OCH3, C7F 13 OCH3, C4F9OCH3, C4F9OC2H5, C4F9CH2CH3, CF3CH2OCF2CF2CF2H, CF3CF(CH2CF3)CF(OCH3)CF2CF3, CF2HCF2OCH2CF3 and a mixture thereof.

[0087] Examples of the mixture include a mixture of CF3(CF2)3OC2H5 and (CF3)2CFCF2OC2H5, which are isomers of C4F9OCH2CH3 (ethyl nonafluorobutyl ether).

[0088] It should be noted that in the above examples, the subscript letters m and n each independently represent an integer from 1 to 20.

[0089] Examples of organic hydrocarbon-based 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).

[0090] With a view to fully providing the effects of the present invention, the concentration of the fluorine-containing polymer of the present invention, which is contained in the surface treatment agent of the present invention, is preferably from 0.1 to 10 wt% and more preferably from 1 to 5 wt% of the total amount of the surface treatment agent of the present invention.

[0091] The solvent content is not specifically limited, however, with regard to handling properties and the like as a surface treatment agent, it is preferably 80% by mass or more of the total amount of the surface treatment agent of the present invention.

[0092] The surface treatment agent of the present invention may further optionally contain an additive, such as a pH adjusting agent, a rust inhibitor, a dye, a flame retardant, a foam suppressant or an antistatic agent, as well as a polymer or resin that is different from the fluorine-containing polymer of the present invention, within a range that does not impair the effects of the present invention.

[0093] Examples of a method for producing the surface treatment agent of the present invention include a method of mixing the fluorine-containing polymer of the present invention, a solvent and an additive, which may optionally be included, such that the surface treatment agent of the present invention is obtained.

[0094] Examples of a method for using the surface treatment agent of the present invention include a method of use in which the surface treatment agent of the present invention is applied to a substrate. By the aforementioned application process, a layer of the surface treatment agent can be formed on the surface of the substrate, and the oil repellency of the substrate's surface can be improved. Furthermore, the aforementioned application process can also impart excellent water repellency to the surface of the substrate.

[0095] There are no specific limitations to the method for applying the surface treatment agent of the present invention to a substrate. For example, coating or the like may be used.

[0096] After applying the surface treatment agent of the present invention to a substrate, the aforementioned solvent can be removed, for example, under conditions of 10 to 120 °C.

[0097] Examples of materials for the aforementioned substrate include glass, plastics, rubber, metals, and ceramics.

[0098] Specific examples of the aforementioned substrate include household items (such as umbrellas, shoes and bags), molded wet area products (such as bathroom components, sink components and kitchen components), relevant exterior areas of buildings (such as bridge piers, roofs and exterior walls), relevant interior areas (such as floors and interior walls), residential products (such as furniture and household appliances), vehicle bodies (such as ships or watercraft, aircraft or airplanes and motor vehicles, including exterior or interior materials) and electronic substrates. Examples

[0099] The present invention is described in more detail with reference to the following examples. Examples 1 to 15 are examples according to the present invention, and examples 16 to 19 are comparative examples.

[0100] The materials, quantities used, processing details, and processing operations shown in the following examples can be modified appropriately without departing from the essential nature of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0101] Below, the terms “parts” and “%” refer to “mass parts” and “mass %”, unless otherwise stated.

[0102] In this description, in some cases a fluorine-containing compound produced in Example 1 is referred to as Monomer 1, a fluorine-containing polymer produced using Monomer 1 is referred to as Fluorine-containing Polymer 1, and a surface treatment agent containing Fluorine-containing Polymer 1 is referred to as Surface Treatment Agent 1. The same applies to other examples.

[0103] Regarding the compounds used in these examples as starting materials and the like, the aforementioned compounds were purchased unless otherwise stated. < 1 H-NMR measurement>

[0104] A target substance to be measured (each monomer synthesized in the examples according to the present invention) was dissolved in chloroform-d as a deuterated solvent such that the concentration of the target substance to be measured was adjusted to approximately 0.2 wt%. SiMe4 (tetramethylsilane) was used as the standard. The prepared solution was placed in a 1 H-NMR measuring tube transferred.

[0105] The measurement conditions are shown below. Device: JNM-ECZ400R / S1 (manufactured by JEOL Ltd.) Nucleus: Proton Number of scans: 16 Example 1 - Synthesis of a monomer 1

[0106] 9.21 g (51.7 mmol) of 4-trifluoromethoxyphenol and 78 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 7.85 g (77.5 mmol) of triethylamine, 5.61 g (62.0 mmol) of acryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 11.25 g of the desired product.

[0107] The chemical 1 H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 2 - Synthesis of a monomer 2

[0108] 9.21 g (51.7 mmol) of 4-trifluoromethoxyphenol and 60 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 7.85 g (77.5 mmol) of triethylamine, 6.53 g (62.0 mmol) of methacryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 11.45 g of the desired product.

[0109] The chemical 1H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 3 - Synthesis of a monomer 3

[0110] 8.05 g (45.4 mmol) of 4-trifluoromethoxyaniline and 80 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 5.25 g (51.9 mmol) of triethylamine, 3.92 g (43.3 mmol) of acryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 8.38 g of the desired product.

[0111] The chemical 1 H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 4 - Synthesis of a monomer 4

[0112] 9.65 g (54.5 mmol) of 4-trifluoromethoxyaniline and 96 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 5.78 g (57.1 mmol) of triethylamine, 5.43 g (51.9 mmol) of methacryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 11.50 g of the desired product.

[0113] The chemical 1H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 5 - Synthesis of a monomer 5

[0114] 11.51 g (64.6 mmol) of 3-trifluoromethoxyphenol and 90 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 9.81 g (96.9 mmol) of triethylamine, 7.02 g (77.5 mmol) of acryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 14.67 g of the desired product.

[0115] The chemical 1 H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 6 - Synthesis of a monomer 6

[0116] 10.85 g (60.9 mmol) of 3-trifluoromethoxyphenol and 90 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 9.25 g (91.4 mmol) of triethylamine, 8.60 g (82.3 mmol) of methacryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 13.71 g of the desired product.

[0117] The chemical 1H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 7 - Synthesis of a monomer 7

[0118] 9.65 g (54.5 mmol) of 3-trifluoromethoxyaniline and 96 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 7.88 g (77.9 mmol) of triethylamine, 4.70 g (51.9 mmol) of acryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 11.44 g of the desired product.

[0119] The chemical 1 H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 8 - Synthesis of a monomer 8

[0120] 9.86 g (55.7 mmol) of 3-trifluoromethoxyaniline and 104 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 8.05 g (79.5 mmol) of triethylamine, 7.20 g (68.8 mmol) of methacryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 13.85 g of the desired product.

[0121] The chemical 1H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 9 - Synthesis of a monomer 9

[0122] 11.51 g (64.6 mmol) of 2-(trifluoromethoxy)phenol and 120 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 9.81 g (96.9 mmol) of triethylamine, 8.18 g (90.3 mmol) of acryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 14.04 g of the desired product.

[0123] The chemical 1H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 10 - Synthesis of a monomer 10

[0124] 10.85 g (60.9 mmol) of 2-(trifluoromethoxy)phenol and 90 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 9.25 g (91.4 mmol) of triethylamine, 8.92 g (85.4 mmol) of methacryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 14.85 g of the desired product.

[0125] The chemical 1H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 11 - Synthesis of a monomer 11

[0126] 12.07 g (68.1 mmol) of 2-trifluoromethoxyaniline and 120 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 9.85 g (97.3 mmol) of triethylamine, 7.04 g (77.8 mmol) of acryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 13.70 g of the desired product.

[0127] The chemical 1 H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 12 - Synthesis of a monomer 12

[0128] 12.73 g (71.9 mmol) of 2-trifluoromethoxyaniline and 120 mL of dichloromethane were mixed in a four-necked flask, which was then immersed in ice water and cooled. After the dropwise addition of 10.80 g (106.7 mmol) of triethylamine, 10.57 g (101.1 mmol) of methacryloyl chloride were added dropwise, and the temperature of the resulting mixture was allowed to rise to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the resulting mixture was separated into an aqueous layer and an organic layer. The organic layer was washed using an aqueous sodium bicarbonate solution (2.5 wt%) and water, and the solvent was then distilled off under reduced pressure, yielding 13.74 g of the desired product.

[0129] The chemical 1H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 13 - Synthesis of a monomer 13

[0130] 10.00 g (56.2 mmol) of 4-trifluoromethoxyphenol and 56 mL of tetrahydrofuran were mixed in a four-necked flask, and 0.36 g (2.81 mmol) of N,N-diisopropylethylamine and 8.72 g (61.8 mmol) of 2-isocyanatoethyl acrylate were added. The resulting mixture was heated to reflux for 21 hours. The desired product was then separated by column chromatography (hexane / acetone), and the solvent was distilled off under reduced pressure, yielding 16.10 g of the desired product. The yield of the desired product was 89.8%.

[0131] The chemical 1 H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 14 - Synthesis of a monomer 14

[0132] 8.00 g (45.2 mmol) of 4-trifluoromethoxyaniline and 45 mL of tetrahydrofuran were mixed in a four-necked flask, and 7.01 g (49.68 mmol) of 2-isocyanatoethyl acrylate were added. The resulting mixture was heated to reflux for 14 hours. The desired product was then separated by column chromatography (hexane / ethyl acetate), and the solvent was distilled off under reduced pressure, yielding 10.80 g of the desired product. The yield of the desired product was 74.9%.

[0133] The chemical 1 H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. Example 15 - Synthesis of a precursor 15-1

[0134] First, 5.56 g (30.9 mmol) of 4-acetoxybenzoic acid and 56 mL of tetrahydrofuran were mixed in a four-necked flask. 4.01 g (33.7 mmol) of thionyl chloride were added dropwise, and the resulting mixture was heated to reflux. The disappearance of the starting materials was confirmed by gas chromatography (GC). The mixture was then 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. The resulting mixture was stirred overnight. After the disappearance of the starting materials was confirmed by GC, water was added to stop the reaction. Following extraction with ethyl acetate, the organic layer was dried over magnesium sulfate. The resulting 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 dried under reduced pressure, yielding 4.12 g of a precursor 15-1. The reaction scheme for obtaining precursor 15-1 is as follows. - Synthesis of a precursor 15-2

[0135] Then, 4.12 g (12.1 mmol) of precursor 15-1, synthesized as described above, were dissolved in a four-necked flask in a mixed solvent of 24 mL tetrahydrofuran and 24 mL methanol, and a 1:1 mixture of aqueous ammonium chloride (1 mol / L) and aqueous sodium hydroxide (1 mol / L) was added dropwise. The disappearance of the starting materials was confirmed by TLC, whereupon the mixture was neutralized with hydrochloric acid (1 mol / L) and extracted using methylene chloride. The resulting organic layer was concentrated under reduced pressure, yielding 3.72 g of precursor 15-2 as a white solid. The reaction scheme for obtaining precursor 15-2 is as follows. - Synthesis of a monomer 15

[0136] 3.72 g (12.5 mmol) of the precursor 15-2 synthesized as described above were dissolved in 25 mL of methylene chloride in a four-necked flask, and 1.77 g (13.7 mmol) of diisopropylethylamine were added dropwise. Subsequently, 1.24 g (13.7 mmol) of acryloyl chloride were added, and the resulting mixture was stirred at room temperature for 2 hours. After confirming the disappearance of the starting materials by GC, water was added to stop the reaction, and after extraction with methylene chloride, the organic layer was dried over magnesium sulfate. The resulting organic layer was separated by silica gel column chromatography (hexane / methylene chloride) and concentrated under reduced pressure. The crystals obtained were washed with hexane and dried under reduced pressure, yielding 2.48 g of the desired product.

[0137] The chemical 1H-NMR shifts of the compound obtained by the above reaction 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) Based on the above 1 H-NMR results confirmed that the compound obtained by the above reaction had a reaction product structure as shown in the above reaction scheme. [Production of a fluorine-containing polymer] - Production of a fluorine-containing polymer 1

[0138] A reaction vessel was charged with 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 Corporation), purged with nitrogen, and then sealed. A polymerization reaction was carried out at 70 °C for 18 hours, yielding an ethyl acetate solution containing a fluorine-containing polymer 1 as the polymer of monomer 1. The reaction scheme for the above polymerization reaction is as follows.

[0139] A portion of the reaction liquid was collected after 18 hours, and the complete disappearance of the peak originating from monomer 1 was confirmed by gas chromatography, thus establishing that the polymerization reaction had proceeded quantitatively. The same confirmation by the reaction rate described above was also applied in other examples. - Production of fluorine-containing polymers 2, 4 to 11 and 13 to 14

[0140] A fluorine-containing polymer 2 was prepared by carrying out a polymerization in the same manner as in the preparation of the fluorine-containing polymer 1 described above, except that 100 parts of monomer 1 were changed to 100 parts of monomer 2.

[0141] The same applies to the fluorine-containing polymers 4 to 11 and 13 to 14. - Production of a fluorine-containing polymer 3

[0142] A reaction vessel was charged with 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 Corporation), purged with nitrogen, and then sealed. A polymerization reaction was carried out at 70 °C for 18 hours, yielding an ethyl acetate solution containing a fluorine-containing polymer 3. The reaction scheme for the above polymerization reaction is as follows. - Production of a fluorine-containing polymer 12

[0143] A reaction vessel was charged with 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 Corporation), purged with nitrogen, and then sealed. A polymerization reaction was carried out at 70 °C for 18 hours, yielding an ethyl acetate solution containing a fluorine-containing polymer 12. The reaction scheme for the above polymerization reaction is as follows. - Production of a fluorine-containing polymer 15

[0144] A reaction vessel was charged with 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 Corporation), purged with nitrogen, and then sealed. A polymerization reaction was carried out at 70 °C for 18 hours, yielding an ethyl acetate solution containing a fluorine-containing polymer 15. The reaction scheme for the above polymerization reaction is as follows. Comparative example 1

[0145] A reaction vessel was charged with phenyl acrylate (100 parts) as the monomer, ethyl acetate (300 parts), and V-601 (1 part, manufactured by FUJIFILM Wako Pure Chemical Corporation), purged with nitrogen, and then sealed. A polymerization reaction was carried out at 70 °C for 18 hours, yielding an ethyl acetate solution containing poly(phenyl acrylate). The reaction scheme for the above polymerization reaction is as follows. Comparative example 2

[0146] A polymerization was carried out in the same manner as in the above-described comparative example 1, except that 100 parts of phenyl acrylate were changed to 100 parts of phenyl methacrylate, yielding an ethyl acetate solution containing poly(phenyl methacrylate). Comparative example 3

[0147] A reaction vessel was charged with N-phenylacrylamide (100 parts) as the monomer, ethyl acetate (700 parts), and V-601 (1 part, manufactured by FUJIFILM Wako Pure Chemical Corporation), purged with nitrogen, and then sealed. A polymerization reaction was carried out at 70 °C for 18 hours, yielding an ethyl acetate solution containing poly(N-phenylacrylamide). The reaction scheme for the above polymerization reaction is as follows. Comparative example 4

[0148] A polymerization was carried out in the same manner as in the above-described comparative example 1, except that 100 parts of phenyl acrylate were changed to 100 parts of N-phenylmethacrylamide, giving an ethyl acetate solution containing poly(N-phenylmethacrylamide). [Production of a surface treatment agent]

[0149] Ethyl acetate was added to the respective solutions containing the polymers obtained as described above to produce surface treatment compounds containing the polymers and solvents. For each surface treatment compound, the solids concentration of the polymer in the compound was 2% by weight. [Evaluation]<Herstellung von Bewertungsprüfkörpern>

[0150] A glass plate was immersed in each of the surface treatment solutions prepared as described above for 1 minute. After removing the glass plate from the surface treatment solutions, it was dried in a dryer at 120 °C for 5 minutes, yielding an evaluation specimen. <Messung des Kontaktwinkels>

[0151] Water or n-hexadecane (n-HD) was added dropwise to the evaluation specimen obtained as described above, and the contact angle (unit: degrees) of water or n-hexadecane (n-HD) was measured using the DMo-501 contact angle gauge (manufactured by Kyowa Interface Science Co., Ltd.). The contact angle was measured at five points each for water or n-hexadecane, and the average of these measurements was used as the evaluation value.

[0152] The evaluation results are shown in Table 1 along with the structural formula of each monomer. (Evaluation criteria for oil rejection)

[0153] In the present invention, when the contact angle of n-hexadecane is 30 degrees or more, the oil repulsion is considered to be excellent.

[0154] The larger the protruding contact angle in a range of 30 degrees or more, the better the oil repulsion.

[0155] With a view to further improving oil repulsion, it is preferred that the protruding contact angle be 40 degrees or more.

[0156] On the other hand, if the protruding contact angle is less than 30 degrees, the oil repulsion is rated as poor. (Evaluation criteria for water repulsion)

[0157] In this description, water repellency is rated as excellent when the contact angle of water is 80 degrees or more.

[0158] The larger the protruding contact angle is in a range of 80 degrees or more, the better the water repellency.

[0159] With a view to further improving water repellency, it is preferred that the protruding contact angle be 100 degrees or more.

[0160] On the other hand, if the protruding contact angle is less than 80 degrees, the water repellency is rated as poor. Table 1 (Part 1) Example 1 2 3 4 5 6 7 8 Monomer Contact angle (degrees) Water 100 101 103 91 95 93 97 100 n-HD 57 42 60 51 46 36 53 41 Example 9 10 11 12 13 14 15 Monomer Contact angle (degrees) Water 88 87 93 95 98 98 105 n-HD 34 34 31 38 48 48 62 [Table 2] Table 1 (Part 2) Example 16 17 18 19 Monomer Contact angle (degrees) Water 90 87 83 79 n-HD < 10 < 10 < 10 < 10

[0161] Based on the results in Table 1, it was confirmed that the fluorine-containing polymers of the present invention, which have structural units formed by the fluorine-containing compounds of the present invention, and the surface treatment agents of the present invention exhibit the desired effects (Examples 1 to 15).

[0162] On the other hand, the polymers and surface treatment agents that have structural units formed by compounds without trifluoromethoxy groups exhibited poor oil repulsion (Examples 16 to 19). QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 2023-159062

[0002] JP 6670615

[0004]

Claims

[1] Fluorine-containing compound represented by the formula (M) below: where X is an oxygen atom, a sulfur atom or a linkage group represented by formula (A) below; R1 is a phenyl group in which at least one hydrogen atom is substituted with a trifluoromethoxy group; and each of R2, R3 and R4 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, where n is an integer from 0 to 8; Q1 is an oxygen atom or a divalent group represented by -NH-; R is an unbranched or branched alkylene group with 1 to 4 carbon atoms or a phenylene group; and Y is one of linking groups represented by the formulas (y1) to (y4) below, wherein each of R5 and R6 independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a group represented by formula (B) below; and each of R7 and R8 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, where m is an integer from 0 to 8; Q2 is an oxygen atom or a divalent group represented by -NH-; R a an unbranched or branched alkylene group with 1 to 4 carbon atoms or a phenylene group; each of R b , R c and R d independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms; and Z is a linking group represented by the following formula (z1) or (z2), where R e a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. [2] Fluorine-containing compound according to claim 1, wherein the trifluoromethoxy group in R1 is bonded to a para-position of the phenyl group. [3] Fluorine-containing compound according to claim 1, wherein X in formula (M) is a linking group represented by formula (A). [4] Fluorine-containing compound according to claim 3, wherein Y in formula (A) is a linking group represented by formula (y1) or (y2). [5] Fluorine-containing polymer comprising a structural unit formed by the fluorine-containing compound according to any one of claims 1 to 4. [6] Surface treatment agent comprising the fluorine-containing polymer according to claim 5 and a solvent.