Fluorine-containing compound, fluorine-containing polymer, and surface treatment agent using same

Abstract

A surface treatment agent containing a fluorine-containing compound represented by formula (1), a fluorine-containing polymer having a structural unit formed from the fluorine-containing compound, the fluorine-containing polymer, and a solvent. In the formula, X is an oxygen atom, a sulfur atom, or a linking group represented by a prescribed formula, R1 is a phenyl group in which at least one hydrogen atom is substituted by a trifluoromethoxy group, and R2, R3, and R4 are each independently a hydrogen atom or a C1-4 alkyl group.

Description

Technical Field

[0001] This invention relates to fluorinated compounds, fluorinated polymers, and surface treatment agents using the same.

[0002] This application claims priority to Japanese Patent Application No. 2023-159062, filed in Japan on September 22, 2023, the contents of which are incorporated herein by reference. Background Technology

[0003] Conventionally, compositions containing fluorinated polymers and solvents are known as waterproof and moisture-proof coating agents. Furthermore, it is known that the aforementioned fluorinated polymers may contain structural units formed from phenyl (meth)acrylates, etc. (e.g., Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent No. 6670615 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] It is known that compounds containing perfluoroalkyl groups produce perfluorocarboxylic acids during decomposition.

[0009] Among perfluorocarboxylic acids, PFOS (perfluorooctanoic acid) and PFOA (perfluorooctanoic acid) are known to have high chemical stability, but on the other hand, they are also known to be difficult to decompose in the environment and have high bioaccumulation. Therefore, various scientific discussions have been held internationally regarding their target values ​​and benchmarks, and they have gradually become restricted substances in various countries.

[0010] On the other hand, regarding PFHxA (perfluorohexanoic acid) and perfluorocarboxylic acids with shorter carbon chains, compared with PFOS and PFOA, they have been found to have very low biotoxicity and bioaccumulation. Therefore, as an alternative technology, perfluoroalkyl compounds containing decomposition products that become PFHxA or perfluorocarboxylic acids with shorter carbon chains are widely used.

[0011] However, among these alternative compounds, the chemical stability of perfluorocarboxylic acids, which are decomposition products, remains unchanged. With continued release into the environment, their long-term accumulation raises concerns about potential harm to human health and the environment. Therefore, new alternative compounds are needed.

[0012] On the other hand, it is known that compounds containing trifluoromethoxy groups are expected to produce CF3OH during their decomposition process, which are very unstable compounds and therefore readily decompose in the environment (e.g., above -20°C).

[0013] Therefore, the objective of this invention is to provide novel fluorinated compounds having a trifluoromethoxy group and being capable of forming polymers with excellent water and oil repellency.

[0014] Furthermore, the subject of this invention is to provide fluoropolymers and surface treatment agents.

[0015] Solution for solving the problem

[0016] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the problems can be solved by the following configuration.

[0017] [1] A fluorinated compound represented by the following formula (M).

[0018]

[0019] In formula (M), X is an oxygen atom, a sulfur atom or a linking group represented by formula (A) below, R1 is a phenyl group in which at least one hydrogen atom is replaced by a trifluoromethoxy group, and R2, R3 and R4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0020]

[0021] 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 a straight-chain or branched alkylene or phenylene with 1 to 4 carbon atoms, and Y is any of the linking groups represented by formulas (y1) to (y4) below.

[0022]

[0023] In formulas (y2) to (y4), R5 and R6 are each independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or groups represented by formula (B) below, and R7 and R8 are each independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms.

[0024]

[0025] In formula (B), m is an integer from 0 to 8, Q2 is an oxygen atom or a divalent group represented by -NH-, and R a R is a straight-chain or branched alkylene or phenylene group having 1 to 4 carbon atoms. b R c R d Each is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is a linking group represented by the following formula (z1) or (z2).

[0026]

[0027] In equation (z2), R eIt consists of hydrogen atoms or alkyl groups having 1 to 4 carbon atoms.

[0028] [2] According to the fluorinated compound of [1], wherein in R1, the trifluoromethoxy group is bonded to the para position of the phenyl group.

[0029] [3] According to the fluorinated compound of [1] or [2], wherein in the formula (M), X is the linking group represented by the formula (A).

[0030] [4] According to the fluorinated compound of [3], wherein the Y in the formula (A) is the linking group represented by the formula (y1) or (y2).

[0031] [5] A fluoropolymer having a structural unit formed from any one of the fluoro compounds described in [1] to [4].

[0032] [6] A surface treatment agent comprising the fluoropolymer described in [5] and a solvent.

[0033] The effects of the invention

[0034] According to the present invention, novel fluorinated compounds having trifluoromethoxy groups and capable of forming polymers with excellent water and oil repellency can be provided.

[0035] In addition, the present invention can provide fluoropolymers and surface treatment agents. Detailed Implementation

[0036] The present invention will now be described in detail.

[0037] The following description of the constituent elements is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0038] In this specification, the range of values ​​represented by “~” refers to the range including the values ​​recorded before and after “~”.

[0039] In this instruction manual, each ingredient can be used alone or in combination of two or more.

[0040] In this instruction manual, when two or more ingredients are used in combination, unless otherwise specified, the “content” of the ingredient refers to the total content of the two or more ingredients.

[0041] Unless otherwise specified, there are no particular limitations on the manufacturing methods of the components in this specification. For example, conventionally known methods can be cited.

[0042] In this specification, (meth)acrylic acid refers to acrylic acid or methacrylic acid.

[0043] In this specification, the superior water and oil repellency of polymers obtained from the fluorinated compounds of the present invention, the fluorinated polymers of the present invention, or the surface treatment agents of the present invention are also referred to as "superior effects of the present invention".

[0044] [The fluorine-containing compound of the present invention]

[0045] The fluorinated compounds of the present invention will be described below.

[0046] The fluorinated compound of the present invention is the fluorinated compound represented by the following formula (M).

[0047]

[0048] 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. R2 is preferably a hydrogen atom or a methyl group. R3 and R4 are preferably hydrogen atoms.

[0049] Even if the fluorinated compounds or fluorinated polymers of the present invention are accidentally released into the environment, the CF3OH that can be generated from trifluoromethoxy through decomposition is an unstable compound that readily decomposes in the environment (e.g., at temperatures above -20°C), thus significantly reducing the risk of residues in the environment and long-distance migration. It is believed that the fluorinated polymers of the present invention can reduce environmental impact.

[0050] In this invention, X in formula (M) is an oxygen atom, a sulfur atom, or a linking group represented by formula (A) below. From the viewpoint of achieving better results without compromising water and oil repellency, X is preferably a linking group represented by formula (A) below.

[0051] The linking group represented by formula (A) is as follows.

[0052]

[0053] In formula (A), n is an integer from 0 to 8. From the viewpoint of achieving better results without compromising water and oil repellency, n is preferably 0 or 1, and more preferably 0.

[0054] In formula (A), R is a straight-chain or branched alkylene or phenylene with 1 to 4 carbon atoms.

[0055] Examples of straight-chain or branched alkylene compounds with 1 to 4 carbon atoms include straight-chain alkylene compounds such as methylene, ethylene, trimethylene, and tetramethylene; and branched alkylene compounds such as isopropylene and isobutylene.

[0056] When n is 1 or more, from the viewpoint of achieving better results for the present invention without compromising water and oil repellency, R is preferably a straight-chain alkyl or phenylene with 2 to 4 carbon atoms, and more preferably a phenylene.

[0057] In formula (A), Q1 is an oxygen atom or a divalent group represented by -NH-.

[0058] In formula (A), Y is any of the linking groups represented by formulas (y1) to (y4) below.

[0059] It should be noted that when the linking groups represented by formulas (y1) to (y4) are incorporated into Y in formula (A), formulas (y1) to (y4) can be incorporated into Y in formula (A) in the state described below or by reversing left and right, but it is preferable to incorporate the linking groups represented by formulas (y1) to (y4) into Y in formula (A) in the state described below.

[0060]

[0061] In formulas (y2) to (y4), R5 and R6 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group represented by formula (B) below.

[0062] For alkyl groups having 1 to 4 carbon atoms as R5 and R6, examples include methyl, ethyl, propyl and butyl.

[0063] The group represented by formula (B) is as follows.

[0064]

[0065] In equation (B), m is an integer from 0 to 8.

[0066] In formula (B), Ra is a straight-chain or branched alkylene or phenylene with 1 to 4 carbon atoms. Examples of straight-chain or branched alkylenes with 1 to 4 carbon atoms in Ra include straight-chain alkylenes such as methylene, ethylene, trimethylene, and tetramethylene; and branched alkylenes such as isopropylene and isobutylene.

[0067] In formula (B), Q2 is an oxygen atom or a divalent group represented by -NH-.

[0068] In formula (B), Rb, Rc, and Rd are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms that can be used as Rb, Rc, and Rd include methyl, ethyl, propyl, and butyl.

[0069] In formula (B), Z is the linking group represented by formula (z1) or (z2) below. It should be noted that the linking group represented by formula (z1) or (z2) can be incorporated into Z in formula (B) in the state described below.

[0070]

[0071] In equation (z2), R e It is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As R e Alkyl groups with 1 to 4 carbon atoms can be methyl, ethyl, propyl, and butyl.

[0072] In formulas (y2) to (y4), R7 and R8 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms that can be R7 or R8 include methyl, ethyl, propyl, and butyl.

[0073] From the viewpoint of achieving better results in this invention, Y is preferably any of the linking groups represented by formulas (y1) to (y2), more preferably the linking group represented by formula (y1) or the linking group represented by formula (y2) where R5 is a hydrogen atom.

[0074] In this invention, in formula (M), R1 is a phenyl group in which at least one hydrogen atom is replaced by a trifluoromethoxy group.

[0075] In R1, at least one of the five hydrogen atoms in a phenyl group must be replaced by a trifluoromethoxy group. In the aforementioned phenyl group, more than two hydrogen atoms may be replaced by a trifluoromethoxy group.

[0076] In order to demonstrate the effects of the present invention, R1 requires that at least one hydrogen atom of the phenyl group be replaced by a trifluoromethoxy group.

[0077] Trifluoromethoxy groups can be bonded to any of the ortho (o-), meta (m-), or para (p-) positions of the phenyl group described above.

[0078] In R1, from the viewpoint of achieving better results in this invention, it is preferable that the trifluoromethoxy group is bonded to the para position of the aforementioned phenyl group.

[0079] In this 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 alkyl groups having 1 to 4 carbon atoms, such as R2, R3, and R4, include methyl, ethyl, propyl, and butyl.

[0080] From the viewpoint of achieving better results with the present invention, the combination of R2, R3, and R4 is preferably such that all of R2, R3, and R4 are hydrogen atoms, or R2 is a methyl group and R3 and R4 are hydrogen atoms. Most preferably, the combination of all of R2, R3, and R4 is composed of hydrogen atoms.

[0081] Regarding the fluorinated compounds of the present invention, from the viewpoint of having superior effects, specific examples of more preferred structures are shown below.

[0082]

[0083] Examples of methods for synthesizing the fluorinated compounds of the present invention include the following synthesis methods 1 to 2.

[0084] Synthesis Method 1

[0085] When the fluorinated compound of the present invention has formula (y1) or (y2) as Y in formula (M), as a synthetic method 1 corresponding to its synthetic method, for example, a method can be described as reacting trifluoromethoxyphenol, trifluoromethoxyaniline, or a precursor represented by the following formula (pre1) with (meth)acryloyl 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 appropriately.

[0086]

[0087] In formula (pre1), x1 is an oxygen atom or a divalent group represented by -NH-.

[0088] Synthesis Method 2

[0089] When the fluorinated compound of the present invention has formula (y3) or (y4) as Y in formula (M), as a synthetic method 2 corresponding to its synthetic method, for example, a method of reacting trifluoromethoxyphenol or trifluoromethoxyaniline with an isocyanate-containing (meth)acrylate such as ethyl 2-isocyanate of (meth)acrylate in a solvent (e.g., tetrahydrofuran) can be used. In the above reaction, a catalyst (e.g., N,N-diisopropylethylamine, triethylamine, triethylenediamine) can be used. After the reaction, purification can be performed appropriately.

[0090] ·use

[0091] The fluorinated compounds of the present invention can be used, for example, as monomers for manufacturing polymers.

[0092] [The fluoropolymer of the present invention]

[0093] The fluoropolymer of the present invention is a fluoropolymer having structural units formed from the fluorinated compounds of the present invention.

[0094] There are no particular limitations on the structural units of the fluoropolymers of the present invention, as long as they include structural units formed by the fluorocompounds of the present invention.

[0095] The structural unit formed by the fluorinated compound of the present invention has a double bond cleavage structure as shown in formula (M) above. The structural unit formed by the fluorinated compound of the present invention has a phenyl group derived from R1 in formula (M) above, wherein at least one hydrogen atom is replaced by a trifluoromethoxy group.

[0096] The fluoropolymers of the present invention can be two or more structural units formed by the fluorocompounds of the present invention, either alone or in combination.

[0097] The fluoropolymers of the present invention may further have structural units other than those formed by the fluorinated compounds of the present invention (other structural units). There are no particular limitations on other structural units as long as they are formed by monomers capable of copolymerizing with the fluorinated compounds of the present invention.

[0098] From the perspective of reducing environmental burden, the fluoropolymers of the present invention preferably do not contain structural units containing perfluoroalkyl groups other than trifluoromethoxy groups.

[0099] Furthermore, from the viewpoint of maintaining water-repellent and oil-repellent properties, relative to the total mass of all structural units of the fluoropolymer of the present invention, it is preferable to include 50% by mass and 100% by mass of structural units formed by the fluorocompound of the present invention, more preferably 80% by mass and more preferably 90% by mass and more preferably.

[0100] The mass-average molecular weight of the fluoropolymer of the present invention is not particularly limited. From the viewpoint of oil resistance and water resistance, the lower limit of the mass-average molecular weight is preferably 10,000 or more, and from the viewpoint of solubility in solvents, the upper limit of the mass-average molecular weight is preferably 1,000,000 or less. It should be noted that the mass-average molecular weight is the weight-average molecular weight determined by gel permeation chromatography (GPC).

[0101] The method for manufacturing the fluoropolymer of the present invention is not particularly limited. As an example of the method for manufacturing the fluoropolymer of the present invention, the fluorinated compound of the present invention can be polymerized in a solvent (e.g., ethyl acetate) in the presence of a polymerization initiator (e.g., dimethyl 2,2'-azobis(2-methylpropionic acid)) at a temperature of 60-80°C, thereby manufacturing the fluoropolymer of the present invention. Furthermore, monomers capable of copolymerizing with the fluorinated compound of the present invention can be further used during polymerization as needed.

[0102] The fluoropolymers of the present invention may, for example, use surface treatment agents.

[0103] [The surface treatment agent of the present invention]

[0104] The surface treatment agent of the present invention is a surface treatment agent containing the fluoropolymer and solvent of the present invention. The surface treatment agent of the present invention exhibits excellent water and oil repellency, and therefore can be used as a water and oil repellent composition and a water and oil repellent agent.

[0105] There are no particular restrictions on the fluoropolymer contained in the surface treatment agent of the present invention, as long as it is a fluoropolymer of the present invention.

[0106] There are no particular limitations on the solvent contained in the surface treatment agent of the present invention, as long as it can disperse and / or dissolve the fluoropolymer of the present invention.

[0107] Examples of solvents include fluorinated solvents, hydrocarbon organic solvents, esters (ethyl acetate, butyl acetate, etc.), and ketones (acetone, methyl ethyl ketone, etc.).

[0108] Examples of fluorinated solvents include hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs).

[0109] Specific examples of fluorinated solvents include m-bis(trifluoromethyl)benzene, p-bis(trifluoromethyl)benzene, CF3CH2CF2CH3, CF3CH2CF2H, and 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 and mixtures thereof.

[0110] As a mixture, for example, a mixture of CF3(CF2)3OC2H5 and (CF3)2CFCF2OC2H5, which are isomers of C4F9OCH2CH3 (ethyl nonafluorobutyl ether), can be cited.

[0111] It should be noted that in the above examples, the subscripts m and n each independently represent integers from 1 to 20.

[0112] Examples of hydrocarbon-based organic solvents include aromatic hydrocarbons (xylene, toluene, ethylbenzene, etc.), alicyclic hydrocarbons (cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, etc.), and chain aliphatic hydrocarbons (hexane, heptane, octane, decane, etc.).

[0113] From the viewpoint of fully utilizing the effects of the present invention, the concentration of the fluoropolymer contained in the surface treatment agent of the present invention is preferably 0.1 to 10% by mass of the total amount of the surface treatment agent of the present invention, more preferably 1 to 5% by mass.

[0114] There is no particular limitation on the content of the solvent, but from the perspective of operability as a surface treatment agent, it is preferably 80% or more of the total amount of the surface treatment agent of the present invention.

[0115] The surface treatment agent of the present invention may, as needed, contain additives such as pH adjusters, rust inhibitors, dyes, flame retardants, defoamers, and antistatic agents, and / or polymers or resins other than the fluoropolymers of the present invention, without impairing the effects of the present invention.

[0116] As a method for manufacturing the surface treatment agent of the present invention, for example, a method can be described by mixing the fluoropolymer of the present invention, a solvent, and additives that may be included as needed to obtain the surface treatment agent of the present invention.

[0117] As a method of using the surface treatment agent of the present invention, an example is the method of applying the surface treatment agent of the present invention to a substrate. By applying it as described above, a layer of surface treatment agent can be formed on the surface of the substrate, improving the oil repellency of the substrate surface. Furthermore, by applying it as described above, excellent water repellency can be further imparted to the surface of the substrate.

[0118] There are no particular limitations on the method of applying the surface treatment agent of the present invention to the substrate. For example, coating is an example.

[0119] After the surface treatment agent of the present invention is applied to the substrate, the solvent can be dried, for example, at a temperature of 10 to 120°C.

[0120] Materials used as the aforementioned substrate include, for example, glass, plastic, rubber, metal, and ceramics.

[0121] Specifically, examples of the aforementioned substrates include daily necessities (umbrellas, shoes, bags, etc.), molded products for water-using areas (bathroom components, washbasin components, kitchen components, etc.), exterior components of buildings (bridge piers, roofs, exterior walls, etc.), interior components (floors, interior walls, etc.), residential products (furniture, home appliances, etc.), vehicle bodies (including exterior or interior materials for ships, airplanes, automobiles, etc.), and electronic substrates.

[0122] Example

[0123] The present invention will be described in more detail below with examples. Examples 1-15 are embodiments, and Examples 16-19 are comparative examples.

[0124] The materials, quantities, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified as long as they do not depart from the spirit of this invention. Therefore, the scope of this invention should not be interpreted as limited by the examples shown below.

[0125] Unless otherwise specified, "parts" and "%" refer to "parts by weight" and "% by weight" respectively.

[0126] In this specification, the fluorinated compound manufactured in Example 1 is sometimes referred to as monomer 1, the fluorinated polymer manufactured using monomer 1 is referred to as fluorinated polymer 1, and the surface treatment agent containing fluorinated polymer 1 is referred to as surface treatment agent 1. This also applies to other examples.

[0127] Regarding the compounds used as raw materials in this embodiment, unless otherwise specified, the compounds were obtained from the market.

[0128] < 1 H-NMR Measurement

[0129] The analyte (corresponding to the monomers synthesized in the examples) was dissolved in the deuterated solvent chloroform-d to prepare a solution with a concentration of approximately 0.2% by mass. SiMe4 (tetramethylsilane) was used as a reference. The prepared solution was transferred to… 1 H-NMR is performed in a measurement tube.

[0130] The measurement conditions are shown below.

[0131] Device: JNM-ECZ400R / S1 (manufactured by Nippon Electronics Co., Ltd.)

[0132] Nuclide: Proton

[0133] Total number of times: 16

[0134] Example 1

[0135] Synthesis of Monomer 1

[0136] 9.21 g (51.7 mmol) of 4-trifluoromethoxyphenol and 78 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 7.85 g (77.5 mmol) of triethylamine was added dropwise, followed by 5.61 g (62.0 mmol) of acryloyl chloride, and the mixture was heated to room temperature. After stirring overnight, the reaction was stopped by adding hydrochloric acid (1 mol / L), and the mixture was separated into an aqueous layer and an organic layer. The obtained organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 11.25 g of the target compound.

[0137]

[0138] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0139] 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)

[0140] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0141] Example 2

[0142] Synthesis of Monomer 2

[0143] 9.21 g (51.7 mmol) of 4-trifluoromethoxyphenol and 60 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 7.85 g (77.5 mmol) of triethylamine was added dropwise, followed by 6.53 g (62.0 mmol) of methacrylamide. The mixture was then heated to room temperature. After stirring overnight, the reaction was stopped by adding hydrochloric acid (1 mol / L), and the mixture was separated into an aqueous layer and an organic layer. The organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 11.45 g of the target compound.

[0144]

[0145] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0146] 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)

[0147] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0148] Example 3

[0149] Synthesis of Monomer 3

[0150] 8.05 g (45.4 mmol) of 4-trifluoromethoxyaniline and 80 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 5.25 g (51.9 mmol) of triethylamine was added dropwise, followed by 3.92 g (43.3 mmol) of acryloyl chloride, and the mixture was heated to room temperature. After stirring overnight, the reaction was stopped by adding hydrochloric acid (1 mol / L), and the mixture was separated into an aqueous layer and an organic layer. The obtained organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 8.38 g of the target compound.

[0151]

[0152] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0153] 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)

[0154] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0155] Example 4

[0156] Synthesis of Monomer 4

[0157] 9.65 g (54.5 mmol) of 4-trifluoromethoxyaniline and 96 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 5.78 g (57.1 mmol) of triethylamine was added dropwise, followed by 5.43 g (51.9 mmol) of methacrylamide. The mixture was then heated to room temperature. After stirring overnight, the reaction was stopped by adding hydrochloric acid (1 mol / L), and the mixture was separated into an aqueous layer and an organic layer. The organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 11.50 g of the target compound.

[0158]

[0159] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0160] 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)

[0161] From the above1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0162] Example 5

[0163] Synthesis of Monomer 5

[0164] 11.51 g (64.6 mmol) of 3-trifluoromethoxyphenol and 90 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 9.81 g (96.9 mmol) of triethylamine was added dropwise, followed by 7.02 g (77.5 mmol) of acryloyl chloride, and the mixture was heated to room temperature. After stirring overnight, the reaction was stopped by adding hydrochloric acid (1 mol / L), and the mixture was separated into an aqueous layer and an organic layer. The obtained organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 14.67 g of the target compound.

[0165]

[0166] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0167] 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)

[0168] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0169] Example 6

[0170] Synthesis of Monomer 6

[0171] 10.85 g (60.9 mmol) of 3-trifluoromethoxyphenol and 90 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 9.25 g (91.4 mmol) of triethylamine was added dropwise, followed by 8.60 g (82.3 mmol) of methacrylamide. The mixture was then heated to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the mixture was separated into an aqueous layer and an organic layer. The organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 13.71 g of the target compound.

[0172]

[0173] The compound obtained through the above reaction 1The chemical shifts of H-NMR are as follows.

[0174] 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)

[0175] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0176] Example 7

[0177] Synthesis of Monomer 7

[0178] 9.65 g (54.5 mmol) of 3-trifluoromethoxyaniline and 96 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 7.88 g (77.9 mmol) of triethylamine was added dropwise, followed by 4.70 g (51.9 mmol) of acryloyl chloride, and the mixture was heated to room temperature. After stirring overnight, the reaction was stopped by adding hydrochloric acid (1 mol / L), and the mixture was separated into an aqueous layer and an organic layer. The obtained organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 11.44 g of the target compound.

[0179]

[0180] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0181] 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)

[0182] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0183] Example 8

[0184] Synthesis of Monomer 8

[0185] 9.86 g (55.7 mmol) of 3-trifluoromethoxyaniline and 104 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 8.05 g (79.5 mmol) of triethylamine was added dropwise, followed by 7.20 g (68.8 mmol) of methacrylamide. The mixture was then heated to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the mixture was separated into an aqueous layer and an organic layer. The organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 13.85 g of the target compound.

[0186]

[0187] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0188] 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)

[0189] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0190] Example 9

[0191] Synthesis of Monomer 9

[0192] 11.51 g (64.6 mmol) of 2-trifluoromethoxyphenol and 120 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 9.81 g (96.9 mmol) of triethylamine was added dropwise, followed by 8.18 g (90.3 mmol) of acryloyl chloride, and the mixture was heated to room temperature. After stirring overnight, the reaction was stopped by adding hydrochloric acid (1 mol / L), and the mixture was separated into an aqueous layer and an organic layer. The obtained organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 14.04 g of the target compound.

[0193]

[0194] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0195] δ (ppm):6.07(dd,1H,CH),6.34(dd,1H,CH),6.65(dd,1H,CH),7.31(m,4H,4CH)

[0196] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0197] Example 10

[0198] Synthesis of Monomer 10

[0199] 10.85 g (60.9 mmol) of 2-trifluoromethoxyphenol and 90 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 9.25 g (91.4 mmol) of triethylamine was added dropwise, followed by 8.92 g (85.4 mmol) of methacrylamide. The mixture was then heated to room temperature. After stirring overnight, hydrochloric acid (1 mol / L) was added to stop the reaction, and the mixture was separated into an aqueous layer and an organic layer. The organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 14.85 g of the target compound.

[0200]

[0201] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0202] δ (ppm):2.07(m,3H,CH3),5.80(m,1H,CH),6.38(m,1H,CH),7.30(m,4H,4CH)

[0203] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0204] Example 11

[0205] Synthesis of Monomer 11

[0206] 12.07 g (68.1 mmol) of 2-trifluoromethoxyaniline and 120 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 9.85 g (97.3 mmol) of triethylamine was added dropwise, followed by 7.04 g (77.8 mmol) of acryloyl chloride, and the mixture was heated to room temperature. After stirring overnight, the reaction was stopped by adding hydrochloric acid (1 mol / L), and the mixture was separated into an aqueous layer and an organic layer. The obtained organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 13.70 g of the target compound.

[0207]

[0208] The compound obtained through the above reaction 1The chemical shifts of H-NMR are as follows.

[0209] 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)

[0210] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0211] Example 12

[0212] Synthesis of Monomer 12

[0213] 12.73 g (71.9 mmol) of 2-trifluoromethoxyaniline and 120 mL of dichloromethane were mixed in a four-necked flask and cooled by immersion in ice water. 10.80 g (106.7 mmol) of triethylamine was added dropwise, followed by 10.57 g (101.1 mmol) of methacrylamide. The mixture was then heated to room temperature. After stirring overnight, the reaction was stopped by adding hydrochloric acid (1 mol / L), and the mixture was separated into an aqueous layer and an organic layer. The obtained organic layer was washed with an aqueous solution of sodium bicarbonate (2.5% by mass) and water, and the solvent was removed by vacuum distillation to obtain 13.74 g of the target compound.

[0214]

[0215] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0216] 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)

[0217] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0218] Example 13

[0219] Synthesis of Monomer 13

[0220] In a four-necked flask, 10.00 g (56.2 mmol) of 4-trifluoromethoxyphenol and 56 mL of tetrahydrofuran were mixed, followed by the addition of 0.36 g (2.81 mmol) of N,N-diisopropylethylamine and 8.72 g (61.8 mmol) of ethyl 2-isocyanate acrylate. The mixture was heated under reflux for 21 hours. The target compound was then separated by column chromatography (hexane / acetone), and the solvent was removed by vacuum distillation to obtain 16.10 g of the target compound. The yield of the target compound was 89.8%.

[0221]

[0222] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0223] 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)

[0224] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0225] Example 14

[0226] Synthesis of Monomer 14

[0227] In a four-necked 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 ethyl 2-isocyanate acrylate was added. The mixture was heated under reflux for 14 hours. The target compound was then separated by column chromatography (hexane / ethyl acetate), and the solvent was removed by vacuum distillation to obtain 10.80 g of the target compound. The yield of the target compound was 74.9%.

[0228]

[0229] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0230] 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)

[0231] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0232] Example 15

[0233] Synthesis of precursor 15-1

[0234] First, 5.56 g (30.9 mmol) of 4-acetoxybenzoic acid and 56 mL of tetrahydrofuran were mixed in a four-necked flask, and 4.01 g (33.7 mmol) of thionyl chloride was added dropwise, followed by reflux. After confirming the disappearance of the starting material 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, followed by stirring overnight. After confirming the disappearance of the starting material by GC, water was added to stop the reaction, and the mixture was extracted with ethyl acetate and dried over magnesium sulfate. The resulting organic layer was separated by silica gel column chromatography (hexane / ethyl acetate) and concentrated under reduced pressure. The crystals were recrystallized using methylene chloride and hexane, and dried under reduced pressure to give 4.12 g of precursor 15-1. The reaction formula for obtaining precursor 15-1 is as follows.

[0235]

[0236] Synthesis of precursor 15-2

[0237] Next, in a four-necked flask, 4.12 g (12.1 mmol) of the precursor 15-1 synthesized as described above was dissolved in a mixed solvent of 24 mL tetrahydrofuran and 24 mL methanol. A 1:1 mixture of ammonium chloride aqueous solution (1 mol / L) and sodium hydroxide aqueous solution (1 mol / L) was added dropwise. After confirming the disappearance of the starting material by TLC, the mixture was neutralized with hydrochloric acid (1 mol / L) and extracted with methylene chloride. The resulting organic layer was concentrated under reduced pressure to give 3.72 g of a white solid, precursor 15-2. The reaction formula for obtaining precursor 15-2 is as follows.

[0238]

[0239] Synthesis of Monomer 15

[0240] In a four-necked 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. Next, 1.24 g (13.7 mmol) of acryloyl chloride was added, and the mixture was stirred at room temperature for 2 hours. After confirming the disappearance of the starting material by GC, water was added to stop the reaction. The mixture was extracted with methylene chloride, and 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 resulting crystals were washed with hexane and dried under reduced pressure to give 2.48 g of the target compound.

[0241]

[0242] The compound obtained through the above reaction 1 The chemical shifts of H-NMR are as follows.

[0243] 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)

[0244] From the above 1 The H-NMR results confirmed that the compound obtained by the above reaction has the structure of the reaction product shown in the above reaction formula.

[0245] [Manufacturing of fluoropolymers]

[0246] Manufacturing of fluoropolymer 1

[0247] Monomer 1 (100 parts), ethyl acetate (300 parts), and V-601 (1 part, dimethyl 2,2'-azobis(2-methylpropionic acid), manufactured by Fujifilm and Koko Pure Chemical Industries Co., Ltd.) synthesized in Example 1 as described above were added to a reaction vessel. After nitrogen purging, the vessel was sealed. The polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing the polymer as monomer 1. The reaction formula for the above polymerization reaction is described below.

[0248] A portion of the reaction solution was taken 18 hours later, and gas chromatography confirmed that the peak originating from monomer 1 had completely disappeared, thus indicating that the polymerization reaction was proceeding quantitatively. This confirmation based on reaction rate was also applied in other examples.

[0249]

[0250] Manufacturing of fluoropolymers 2, 4~11, 13~14

[0251] The 100 parts of monomer 1 are replaced with 100 parts of monomer 2, and otherwise polymerized in the same manner as the above-mentioned fluoropolymer 1 to produce fluoropolymer 2.

[0252] The same applies to fluoropolymers 4~11 and 13~14.

[0253] Manufacturing of fluoropolymer 3

[0254] Monomer 3 (100 parts), ethyl acetate (700 parts), and V-601 (1 part, manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.) synthesized in Example 3 as described above were added to a reaction vessel. After nitrogen purging, the vessel was sealed. The polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing fluoropolymer 3. The reaction formula for the above polymerization reaction is as follows.

[0255]

[0256] Manufacturing of fluoropolymer 12

[0257] Monomer 12 (100 parts), ethyl acetate (400 parts), and V-601 (1 part, manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.) synthesized in Example 12 as described above were added to a reaction vessel. After nitrogen purging, the vessel was sealed. The polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing fluoropolymer 12. The reaction formula for the above polymerization reaction is described below.

[0258]

[0259] Manufacturing of fluoropolymer 15

[0260] Monomer 15 (100 parts), ethyl acetate (500 parts), and V-601 (1 part, manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.) synthesized in Example 15 as described above were added to a reaction vessel. After nitrogen purging, the vessel was sealed. The polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing fluoropolymer 15. The reaction formula for the above polymerization reaction is described below.

[0261]

[0262] Comparative Example 1

[0263] 100 parts of phenyl acrylate, 300 parts of ethyl acetate, and 1 part of V-601 (manufactured by Fujifilm and Kojun Chemical Co., Ltd.) were added as monomers to a reaction vessel. After nitrogen purging, the vessel was sealed. The polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing phenyl acrylate. The reaction formula for the above polymerization reaction is described below.

[0264]

[0265] Comparative Example 2

[0266] The 100 parts of phenyl acrylate were replaced with 100 parts of phenyl methacrylate, and the polymerization was carried out in the same manner as in Comparative Example 1 above to obtain an ethyl acetate solution containing polyphenyl methacrylate.

[0267] Comparative Example 3

[0268] 100 parts of N-phenylacrylamide, 700 parts of ethyl acetate, and 1 part of V-601 (manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd.) were added as monomers to a reaction vessel. After nitrogen purging, the vessel was sealed. The polymerization reaction was carried out at 70°C for 18 hours to obtain an ethyl acetate solution containing poly(N-phenylacrylamide). The reaction formula for the above polymerization reaction is described below.

[0269]

[0270] Comparative Example 4

[0271] The 100 parts of phenyl acrylate were replaced with 100 parts of N-phenylmethylacrylamide, and the polymerization was carried out in the same manner as in Comparative Example 1 above to obtain an ethyl acetate solution containing poly(N-phenylmethylacrylamide).

[0272] [Manufacturing of surface treatment agents]

[0273] Ethyl acetate is added to the solution containing each polymer obtained as described above to prepare a surface treatment agent containing both polymer and solvent. The solid content concentration of the polymer in any surface treatment agent is 2% by mass of the surface treatment agent.

[0274] [evaluate]

[0275] <Preparation of Evaluation Test Pieces>

[0276] Immerse the glass plate in the surface treatment agents prepared as described above for 1 minute. After removing the glass plate from the surface treatment agents, dry the glass plate in a dryer at 120°C for 5 minutes to obtain the evaluation test piece.

[0277] <Determination of contact angle>

[0278] Water or n-hexadecane (n-HD) was added to the evaluation test piece obtained as described above, and the contact angle (in degrees) 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 5 points each with water and n-hexadecane, and the average value was taken as the evaluation value.

[0279] The evaluation results, along with the structural formulas of each monomer, are shown in Table 1.

[0280] (Evaluation criteria for oil repellency)

[0281] In this invention, the oil repellency is excellent when the contact angle of n-hexadecane is 30 degrees or more.

[0282] The greater the contact angle is than 30 degrees, the better the oil repellency.

[0283] From the perspective of superior oil repellency, a contact angle of 40 degrees or higher is preferred.

[0284] On the other hand, when the contact angle is less than 30 degrees, it is evaluated as having poor oil repellency.

[0285] (Evaluation criteria for water repellency)

[0286] In this specification, the water repellency is excellent when the water contact angle is greater than 80 degrees.

[0287] The greater the contact angle is than 80 degrees, the better the water repellency.

[0288] From the perspective of superior water repellency, a contact angle of 100 degrees or more is preferred.

[0289] On the other hand, when the contact angle is less than 80 degrees, it is evaluated as having poor water repellency.

[0290] [Table 1]

[0291]

[0292] [Table 2]

[0293]

[0294] The results in Table 1 confirm that the fluoropolymers of the present invention and the surface treatment agents of the present invention, which have structural units formed by the fluorinated compounds of the present invention, exhibit the desired effects (Examples 1-15).

[0295] On the other hand, polymers and surface treatment agents with structural units formed from compounds that do not have trifluoromethoxy groups have poor oil repellency (Examples 16-19).

Claims

1. A fluorine-containing compound represented by the following formula (M), In formula (M), X is an oxygen atom, a sulfur atom or a linking group represented by formula (A) below, R1 is a phenyl group in which at least one hydrogen atom is replaced by a trifluoromethoxy group, and R2, R3 and R4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 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 a straight-chain or branched alkylene or phenylene with 1 to 4 carbon atoms, and Y is any of the linking groups represented by formulas (y1) to (y4) below. In formulas (y2) to (y4), R5 and R6 are each independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or groups represented by formula (B) below, and R7 and R8 are each independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. In formula (B), m is an integer from 0 to 8, Q2 is an oxygen atom or a divalent group represented by -NH-, and R a R is a straight-chain or branched alkylene or phenylene group having 1 to 4 carbon atoms. b R c R d Each is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z is a linking group represented by the following formula (z1) or (z2); In equation (z2), R e It consists of hydrogen atoms or alkyl groups having 1 to 4 carbon atoms.

2. The fluorine-containing compound according to claim 1, wherein, In R1, the trifluoromethoxy group is bonded to the para position of the phenyl group.

3. The fluorinated compound according to claim 1, wherein, In formula (M), X is the linking group represented by formula (A).

4. The fluorinated compound according to claim 3, wherein, In formula (A), Y is the linking group represented by formula (y1) or (y2).

5. A fluoropolymer having structural units formed from any one of the fluoropolymers according to claims 1 to 4.

6. A surface treatment agent comprising the fluoropolymer and solvent of claim 5.

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