Polymer-containing composition, method for producing the same, water and oil repellent agent, and article

Abstract

Provided are a polymer-containing composition that poses low risk to living organisms and the environment and exhibits water and oil repellency equivalent to that of conventional fluorine-containing polymers, a method for producing the same, and a water and oil repellent agent and an article having a coating film thereof on its surface. (A) A compound represented by the following formula (I): [Formula 1] 1. A polymer-containing composition comprising a polymer having as a monomer component a polyfluoroalkyl vinyl compound represented by the formula: TIFF2026036447000019.tif8132 (wherein R is a hydrogen atom or a methyl group, n is a number from 1 to 6, a is a number from 1 to 4, b is a number from 0 to 3, and c is a number from 1 to 3), wherein the content of (B) PFHxA-related substances is 1000 ppb or less relative to the total amount of components (A) and (B), for each of two or more types of substances, when each of the two or more types is present, the content of each of the two or more types is 1000 ppb or less relative to the total amount of components (A) and (B).

Description

[Technical Field]

[0001] The present invention relates to a composition containing a fluorine-containing polymer, in particular a polymer of an acrylic or methacrylic monomer having a polyfluoroalkyl group, a method for producing the same, a water / oil repellent agent containing the polymer as an active ingredient, and an article having a coating of the water / oil repellent agent on its surface. [Background technology]

[0002] Conventionally, in order to provide a substrate with surface modification functions such as water and oil repellency, a coating film made of a polymer of a fluorine-based acrylic or methacrylic monomer has been formed on the surface, as shown in Patent Documents 1 and 2.

[0003] Long-chain perfluoroalkyl groups with eight or more carbon atoms have been used to achieve surface modification functions such as high water and oil repellency. However, perfluorooctanoic acid (PFOA) and its salts, PFOA-related substances, and long-chain perfluorocarboxylic acids with perfluoroalkyl groups with eight or more carbon atoms have been noted to accumulate in the human body.

[0004] In order to reduce the risks to living organisms and the environment, PFOA has been replaced with, for example, perfluorohexanoic acid (PFHxA), which has a carbon number of 6. For example, Patent Document 3 discloses a surface modifier containing, as an active ingredient, a polymer of a (meth)acrylic acid derivative containing a perfluoroalkyl group having a carbon number of 6.

[0005] However, in recent years, the harmful effects of PFHxA, its salts, and PFHxA-related substances have been pointed out, and restrictions on their use are being considered. For example, in Europe, restrictions based on content limits of less than 25 ppb for PFHxA and its salts and less than 1000 ppb for the total of PFHxA-related substances have been proposed.

[0006] One method for complying with the above regulations is to remove such low-molecular-weight compounds from the water / oil repellent. For example, Patent Document 4 discloses a method for reducing the amount of fluorine-containing alcohol by bringing an adsorbent into contact with the repellent containing the fluorine-containing alcohol.

[0007] However, according to the inventors' investigations, it was found that this method does not completely remove the adsorbent that has come into contact with the repellent, and that trace amounts may be mixed into the repellent, or that some of the active ingredient of the repellent may be adsorbed onto the adsorbent, changing the amount of active ingredient in the repellent. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Special Publication No. 1-042983 [Patent Document 2] Japanese Patent Application Publication No. 7-109317 [Patent Document 3] Japanese Patent Application Publication No. 2020-050757 [Patent Document 4] Patent Publication No. 2021-070763 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, an object of the present invention is to provide a polymer-containing composition that poses low risk to living organisms and the environment and exhibits water and oil repellency equivalent to that of conventional fluorine-containing polymers, a method for producing the same, and an article having a water and oil repellent and a coating thereof applied on its surface. [Means for solving the problem]

[0010] As a result of intensive research to achieve the above object, the present inventors have found that by purifying a specific polyfluoroalkylvinyl monomer and then polymerizing it, it is possible to obtain a CF6F6 compound having more than six consecutive perfluorocarbons, which is highly hazardous to living organisms and the environment. 13The present inventors have discovered that a polymer can be obtained that has water and oil repellency equivalent to that of conventional polymers having perfluoroalkyl groups with 8 or more carbon atoms, without using a monomer having a perfluoroalkyl group with more than 8 carbon atoms, and that has a low content of PFHxA-related substances as by-products. This has led to the completion of the present invention.

[0011] That is, the present disclosure provides the following inventions. [1] (A) Formula (I) [ka] (wherein R is a hydrogen atom or a methyl group, n is a number from 1 to 6, a is a number from 1 to 4, b is a number from 0 to 3, and c is a number from 1 to 3), (B) A polymer-containing composition in which the content of PFHxA-related substances, when there are two or more types, is 1000 ppb or less relative to the total amount of components (A) and (B), for all of the contents of each of the two or more types. [2] The component (B) is represented by the following formula (IIa) or (IIb): [ka] (In the formula, X 1 is a monovalent organic group. [ka] (In the formula, X 2 is a monovalent organic group, excluding a fluorine atom, -C(=O)OH, -C(=O)OY (Y is a monovalent organic group), and -CFY (Y is a monovalent organic group). The polymer-containing composition according to [1], which is represented by the formula: [3] The polymer-containing composition according to [2], wherein component (B) is at least one selected from the group consisting of 2-(perfluorohexyl)ethyl iodide (CAS Registry Number: 2043-57-4), 2-(perfluorohexyl)ethanol (CAS Registry Number: 647-42-7), 2-(perfluorohexyl)ethyl acrylate (CAS Registry Number: 17527-29-6), and 2-(perfluorohexyl)ethyl methacrylate (CAS Registry Number: 2144-53-8). [4] The polymer-containing composition according to any one of [1] to [3], wherein the polymer-containing composition contains a fluorine-containing solvent. [5] The polymer-containing composition according to any one of [1] to [4], which does not contain an adsorbent. [6] A water and oil repellent comprising the polymer-containing composition according to any one of [1] to [5]. [7] An article having a coating of the water and oil repellent agent according to [6] on its surface. [8] The article according to [7], which has a substrate having a coating film of the water and oil repellent agent applied to its surface, and the substrate is a fiber. [9] A method for producing the polymer-containing composition according to [1], a purification step of purifying a monomer-containing composition containing the polyfluoroalkyl vinyl compound represented by formula (I) and the component (B) so that the content of each of the components (B), when there are two or more components, is 1000 ppb or less relative to the total amount of the polyfluoroalkyl vinyl compound represented by formula (I) and the component (B); and A method for producing a polymer-containing composition, comprising a polymerization step of subjecting the monomer-containing composition after the purification step to a polymerization reaction in a solvent to obtain a polymer-containing composition.

[10] The component (B) is represented by the following formula (IIa) or (IIb): [ka] (In the formula, X1 is a monovalent organic group. [ka] (In the formula, X 2 is a monovalent organic group excluding a fluorine atom, -C(=O)OH, -C(=O)OY (Y is a monovalent organic group), and -CFY (Y is a monovalent organic group). The method for producing a polymer-containing composition according to [9], wherein the polymer-containing composition is represented by the formula:

[11] The method for producing a polymer-containing composition according to [9] or

[10] , wherein component (B) is at least one selected from the group consisting of 2-(perfluorohexyl)ethyl iodide (CAS Registry Number: 2043-57-4), 2-(perfluorohexyl)ethanol (CAS Registry Number: 647-42-7), 2-(perfluorohexyl)ethyl acrylate (CAS Registry Number: 17527-29-6), and 2-(perfluorohexyl)ethyl methacrylate (CAS Registry Number: 2144-53-8).

[12] The method for producing a polymer-containing composition according to any one of [9] to

[11] , wherein the purification is carried out by molecular distillation.

[13]

[13] The method for producing a polymer-containing composition according to

[12] , wherein the temperature of molecular distillation is 200°C or less.

[14] The method for producing a polymer-containing composition according to

[12] or

[13] , wherein the degree of vacuum in the molecular distillation is 150 Pa or less.

[15] The method for producing a polymer-containing composition according to any one of [9] to

[14] , wherein a polymerization inhibitor is added in an amount of 0.01 to 1000 ppm relative to 100 g of the polyfluoroalkylvinyl compound represented by the formula (I) and molecular distillation is carried out. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a water / oil repellent which poses low risk to living organisms and the environment and exhibits water / oil repellency equivalent to that of conventional fluorine-containing polymers, and an article having a coating film of the water / oil repellent on its surface. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below.

[0014] (Polymer-containing composition) The polymer-containing composition of the present invention comprises (A) a compound represented by the following formula (I): [ka] (wherein R is a hydrogen atom or a methyl group, n is a number from 1 to 6, a is a number from 1 to 4, b is a number from 0 to 3, and c is a number from 1 to 3), the polymer (hereinafter also referred to as component (A) or polymer (A)) having as a monomer component a polyfluoroalkyl vinyl compound represented by the following formula: (wherein R is a hydrogen atom or a methyl group, n is a number from 1 to 6, a is a number from 1 to 4, b is a number from 0 to 3, and c is a number from 1 to 3). The content of (B) PFHxA-related substances (hereinafter also referred to as component (B)) is 1000 ppb or less relative to the total amount of components (A) and (B), for each of the contents of two or more kinds.

[0015] In the polymer-containing composition of the present invention, component (A) is an active ingredient of a water / oil repellent, etc. The polyfluoroalkylvinyl compound represented by formula (I), which is a monomer component used as a raw material for polymer (A), has a perfluoroalkyl group having 6 or less carbon atoms at one molecular chain end and an acryloxy group or methacryloxy group at the other molecular chain end.

[0016] The polyfluoroalkylvinyl compound represented by formula (I) not only has a molecular chain terminal composed of a perfluoroalkyl group having 6 or less carbon atoms, which has low bioaccumulation properties, but also has a -CH2CF2- group derived from vinylidene fluoride along the molecular chain, which easily releases hydrogen H and fluorine F as HF to form a double bond, which is easily decomposed by ozonolysis and biodegraded to a compound with a smaller number of carbon atoms. Therefore, polymer (A) containing the polyfluoroalkylvinyl compound represented by formula (I) as a monomer component has little environmental impact and yet has performance equivalent to conventional fluorine-containing polymers, and can therefore be suitably used as an active ingredient in surface modifiers such as water and oil repellents and release agents.

[0017] In formula (I), n is a number from 1 to 6, a is a number from 1 to 4, b is a number from 0 to 3, and c is a number from 1 to 3. From the viewpoints of the stability of the polymerization solution during polymerization, the solubility, the polymerization rate, and the surface modification performance of the polymer (A), preferably, n is a number from 2 to 4, a is a number from 1 to 2, b is a number from 1 to 3, and c is a number from 1 to 2.

[0018] Examples of the polyfluoroalkylvinyl compound represented by formula (I) include those represented by the following formula: [ka]

[0019] [ka]

[0020] The polyfluoroalkylvinyl compound represented by formula (I) may be used as a monomer component of polymer (A) either alone or as a mixture of two or more.

[0021] The PFHxA-related substance, which is component (B) of the present invention, is a substance that decomposes into PFHxA (perfluorohexanoic acid), and is C5F 11 - is attached to another carbon atom, or a linear or branched perfluoropentyl group (including salts and polymers) related substance, or C6F 13 - linear or branched perfluorohexyl group (including salts and polymers) related substances, among which C6F 13 X (X excludes a fluorine atom, —C(═O)OH, —C(═O)OY (Y is a monovalent organic group), and —CFY (Y is a monovalent organic group). PFHxA-related substances are generally represented by the following formula (IIa) or (IIb). [ka] (In the formula, X 1 is a monovalent organic group. [ka] (In the formula, X 2 is a monovalent organic group, excluding a fluorine atom, —C(═O)OH, —C(═O)OY (where Y is a monovalent organic group), and —CF2Y (where Y is a monovalent organic group).

[0022] X 1 Examples of such groups include —CH2CH2C(═O)OH and —CH2CH2OH.

[0023] X 2 Examples of the alkyl group include an iodine atom, —CH2CH2I, —CH2CH2OH, —CH2CH2OC(=O)CH=CH2, and —CH2CH2OC(=O)C(CH3)=CH2.

[0024] Specific examples of PFHxA-related substances include 2-(perfluorohexyl)ethyl iodide (CAS Registry Number: 2043-57-4), 2-(perfluorohexyl)ethanol (CAS Registry Number: 647-42-7), 2-(perfluorohexyl)ethyl acrylate (CAS Registry Number: 17527-29-6), 2-(perfluorohexyl)ethyl methacrylate (CAS Registry Number: 2144-53-8), perfluorohexyl iodide (CAS Registry Number: 355-43-1), and perfluorohexylethylene (CAS Registry Number: 25291-17-2). Among these, 2-(perfluorohexyl)ethyl iodide, 2-(perfluorohexyl)ethanol, 2-(perfluorohexyl)ethyl acrylate, and 2-(perfluorohexyl)ethyl methacrylate are particularly produced as by-products in the synthesis process of the polyfluoroalkyl vinyl compound represented by formula (I), and are often contained in the composition.

[0025] In the polymer-containing composition of the present invention, the content of PFHxA-related substances as component (B), when two or more types are present, may be 1000 ppb or less, preferably 500 ppb or less, more preferably 300 ppb or less, even more preferably 100 ppb or less, particularly preferably 10 ppb or less, and most preferably 1 ppb or less, relative to the total amount of components (A) and (B). The lower limit of the content of PFHxA-related substances is not particularly limited and may be 0 ppb. Considering the application of various known separation and purification methods under typical conditions, the lower limit is, for example, 0 ppb or more, 1 ppb or more, or 10 ppb or more.

[0026] In the polymer-containing composition of the present invention, the total content of PFHxA-related substances (component (B)) relative to the total amount of components (A) and (B) is preferably 1000 ppb or less, more preferably 700 ppb or less, even more preferably 500 ppb or less, even more preferably 100 ppb or less, particularly preferably 10 ppb or less, and most preferably 1 ppb or less. The lower limit of the total content of PFHxA-related substances is not particularly limited and may be 0 ppb. Considering the application of various known separation and purification methods under typical conditions, the lower limit is, for example, 0 ppb or more, 1 ppb or more, or 10 ppb or more.

[0027] The method for measuring the content of PFHxA-related substances is not particularly limited, but reference can be made to "BS EN 17681-1:2022", "BS EN 17681-2:2022", "CEN / TS 15968:2010", etc.

[0028] Furthermore, the polymer-containing composition of the present invention preferably does not contain an adsorbent, which can prevent a trace amount of adsorbent from being mixed into the composition, causing a portion of the active ingredient (A) of the composition to be adsorbed onto the adsorbent, thereby preventing a change in the amount of the active ingredient in the water / oil repellent.

[0029] Examples of the adsorbent include activated carbon and ion exchange resins.

[0030] The polymer-containing composition of the present invention may contain other components in addition to the components (A) and (B). Examples of such other components include, but are not limited to, solvents, other water and oil repellents, crosslinking agents, fillers, surfactants, antifoaming agents, sizing agents, antibacterial agents, mildew inhibitors, wrinkle inhibitors, softeners, flame retardants, antistatic agents, insect repellents, pigments, antioxidants, emulsifiers, and pH adjusters. When a solvent is used, the content of the component (A) in the polymer-containing composition of the present invention (polymer concentration) is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and even more preferably 3 to 15% by mass, from the viewpoint of, for example, coatability onto a substrate surface.

[0031] (Method of producing polymer-containing composition) The polymer-containing composition of the present invention described above can be produced by a method comprising the following steps: a purification step of purifying a monomer-containing composition containing the polyfluoroalkyl vinyl compound represented by formula (I) and the component (B) to reduce the content of the component (B) relative to the polyfluoroalkyl vinyl compound represented by formula (I); and A polymerization step in which the monomer-containing composition after the purification step is subjected to a polymerization reaction in a solvent to obtain a polymer-containing composition.

[0032] By purifying the monomer-containing composition containing the polyfluoroalkyl vinyl compound represented by formula (I) and the component (B) in this manner and then polymerizing it, the monomer-containing composition in the purification step has a relatively low viscosity, making it easy to handle and enabling it to be purified using various known separation and purification methods.

[0033] As the purification method in the purification step, various known separation and purification methods can be used. Examples of purification methods include column chromatography and distillation. However, since the polyfluoroalkylvinyl compound represented by formula (I) and component (B) have similar chemical structures, a large amount of eluent or packing material must be used for good purification by column chromatography, which is unsuitable for industrial production. On the other hand, distillation does not require an eluent or packing material, and is therefore preferable from the viewpoint of industrial production. Preferred distillation methods include simple distillation, rectification, and molecular distillation, and among these, molecular fractional distillation is particularly preferable from the viewpoint of excellent productivity.

[0034] Since molecular distillation is carried out under reduced pressure, purification can be performed at a relatively low temperature, which makes it suitable for purifying compounds that may polymerize when exposed to high temperatures, such as the polyfluoroalkylvinyl compound of the present invention.

[0035] The apparatus used for molecular distillation can be any conventionally known apparatus, and is not particularly limited. For example, a pot-type molecular distillation apparatus, a falling film molecular distillation apparatus, a centrifugal molecular distillation apparatus, a thin film distillation apparatus, and a thin film evaporator can be used.

[0036] The temperature of the molecular distillation is preferably 200° C. or lower, more preferably 50 to 200° C., even more preferably 60 to 100° C., particularly preferably 65 to 95° C., and especially preferably 70 to 90° C. The degree of vacuum in the molecular distillation is preferably 150 Pa or lower, more preferably 0.1 to 150 Pa, even more preferably 1.0 to 100 Pa, particularly preferably 5.0 to 80 Pa, and especially preferably 10 to 60 Pa. When the temperature and degree of vacuum are within these ranges, the polyfluoroalkylvinyl compound represented by formula (I) can be purified with a good recovery rate.

[0037] When the polyfluoroalkylvinyl compound represented by formula (I) is subjected to molecular distillation, it is preferable to add a polymerization inhibitor.

[0038] Examples of polymerization inhibitors include hydroquinone, 4-methoxyphenol, benzoquinone, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-tert-butylcatechol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, di-tert-butyl-p-cresol, pyrogallol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). These polymerization inhibitors may be used alone or in combination of two or more. Among them, 4-methoxyphenol is preferred.

[0039] The amount of polymerization inhibitor added is preferably 0.01 to 1000 ppm, more preferably 0.1 to 500 ppm, and even more preferably 1 to 200 ppm, relative to 100 g of the polyfluoroalkylvinyl compound represented by formula (I). If the amount added is less than 0.01 ppm, the polyfluoroalkylvinyl compound represented by formula (I) may polymerize during molecular distillation, while if the amount added is more than 1000 ppm, polymerization may not proceed in the polymerization step of polymerizing the polyfluoroalkylvinyl compound represented by formula (I) after molecular distillation.

[0040] In the monomer-containing composition purified by the above method, the content of PFHxA-related substances (B), which is component (B), in the case of two or more types, may be 1000 ppb or less, preferably 500 ppb or less, more preferably 300 ppb or less, even more preferably 100 ppb or less, particularly preferably 10 ppb or less, and most preferably 1 ppb or less, relative to the total amount of the polyfluoroalkyl vinyl compound represented by formula (I) and component (B), in all of the contents of each type. The lower limit of the content of PFHxA-related substances is not particularly limited and may be 0 ppb. Considering the application of various known separation and purification methods under typical conditions, the lower limit is, for example, 0 ppb or more, 1 ppb or more, or 10 ppb or more.

[0041] In the monomer-containing composition purified by the above method, the total content of PFHxA-related substances (component (B)) relative to the total amount of the polyfluoroalkylvinyl compound represented by formula (I) and component (B) is preferably 1000 ppb or less, more preferably 700 ppb or less, even more preferably 500 ppb or less, even more preferably 100 ppb or less, particularly preferably 10 ppb or less, and most preferably 1 ppb or less. The lower limit of the total content of PFHxA-related substances is not particularly limited and may be 0 ppb. Considering the application of various known separation and purification methods under typical conditions, the lower limit is, for example, 0 ppb or more, 1 ppb or more, or 10 ppb or more.

[0042] The method for measuring the content of PFHxA-related substances is not particularly limited, but reference can be made to "BS EN 17681-1:2022", "BS EN 17681-2:2022", "CEN / TS 15968:2010", etc.

[0043] In the polymerization step after the purification step, the polyfluoroalkylvinyl compound represented by formula (I) in the monomer-containing composition can be obtained by polymerizing it using a radical reaction initiator by a known method such as solution polymerization.

[0044] The solvent used in the polymerization step is not particularly limited as long as it can dissolve the polyfluoroalkylvinyl compound represented by formula (I), but a fluorine-based solvent is preferred. Examples of fluorine-based solvents include Novec 7300, Novec 7200, Novec 7100 (manufactured by 3M), AC-6000, AE-3000 (manufactured by AGC Inc.), hexafluoroacetone, hexafluoroisopropanol, and m-xylene hexafluoride (manufactured by Central Glass Co., Ltd.). Among them, Novec 7300 is preferred from the viewpoint of solubility. The amount of the solvent used is not particularly limited, but is preferably 50 to 2000 parts by mass, more preferably 100 to 1000 parts by mass, and even more preferably 200 to 400 parts by mass, per 100 parts by mass of the polyfluoroalkylvinyl compound represented by formula (I).

[0045] Examples of radical polymerization initiators that can be used in the polymerization step include dimethyl azobisisobutyrate (V-601), cumene hydroperoxide, succinic acid peroxide, di-t-butyl peroxide, diisobutyryl peroxide, diisobutyl peroxydicarbonate, dicumyl peroxide, cyclohexanone peroxide, dimethyl-2,2'-azobisisobutyrate, benzoyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, 2,2'-azobis(2-methylamidoxime) dihydrochloride, 2,2'-azobis(2-methylbutyronitrile) (V-59), 2,2'-azobis(isobutylamidine) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] and its disulfate, 2,2'-azobisisobutyronitrile (AIBN), 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethylhexane-2,5-dihydroperoxide, t-butyl-α-cumyl peroxide, t-butyl peroxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxyisopropyl carbonate, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)-p-diisopropylbenzene, and other azo compounds and organic peroxides, potassium persulfate, sodium persulfate, and ammonium persulfate. These radical polymerization initiators may be used alone or in combination of two or more.

[0046] The amount of radical polymerization initiator used is not particularly limited, but is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the polyfluoroalkylvinyl compound represented by formula (I).

[0047] The polymerization conditions for the polyfluoroalkylvinyl compound represented by formula (I) using the solvent and radical polymerization initiator are preferably an inert gas atmosphere at 40 to 120°C, particularly 65 to 75°C, for 4 to 30 hours, particularly 18 to 24 hours.

[0048] This reaction is preferably carried out in an organic solvent such as a partially fluorinated solvent such as Novec 7300, Novec 7200, or Novec 7100 (manufactured by 3M) or m-xylene hexafluoride, or an acetate ester such as ethyl acetate or butyl acetate, or a ketone such as methyl ethyl ketone or methyl isobutyl ketone. In some cases, the reaction may be carried out in a mixed solvent of the above-mentioned solvent with a lower monohydric alcohol such as methanol, ethanol, propanol, or butanol, or in the presence of a chain transfer agent such as a mercaptan.

[0049] The weight average molecular weight (Mw) of the polymer (A) thus obtained is preferably about 2,000 to 2,000,000, more preferably 10,000 to 500,000, as measured by high performance liquid chromatography.

[0050] (Water and oil repellent) The water / oil repellent of the present invention comprises the polymer-containing composition of the present invention described above. The water / oil repellent of the present invention is usually provided as a polymer-containing composition, which is a solvent solution containing the polymer of component (A). Here, the content of component (A) in the solvent solution (polymer concentration) is preferably 1 to 50 mass%, more preferably 3 to 30 mass%, and even more preferably 3 to 15 mass%.

[0051] The solvent used in the water / oil repellent of the present invention is not particularly limited as long as it can dissolve the monomer represented by formula (I) and the polymer of component (A), but fluorine-based solvents are preferred. Examples of fluorine-based solvents include Novec 7300, Novec 7200, and Novec 7100 (manufactured by 3M), AC-6000 and AE-3000 (manufactured by AGC Inc.), hexafluoroacetone, hexafluoroisopropanol, and m-xylene hexafluoride (manufactured by Central Glass Co., Ltd.). Among these, Novec 7300 is preferred from the viewpoint of solubility. The solvent used in the method for producing the polymer-containing composition described above may be used as the solvent for the water / oil repellent of the present invention. Alternatively, the solvent may be added after the production of the polymer of component (A) to adjust the concentration of the polymer of component (A).

[0052] (Goods) The article of the present invention has a surface coated with the water / oil repellent agent of the present invention. The article of the present invention preferably has a substrate having a surface coated with the water / oil repellent agent. The water / oil repellent agent of the present invention easily and firmly adheres to substrates such as fibers, glass, paper, porous materials, plastics, and metals, forming a cured film as a coated film. This cured film exhibits excellent water / oil repellency and is non-adhesive due to the fluorine atoms contained in the polymer of component (A). Therefore, it is suitable for use as a substrate for an article, such as fibers, paper, or porous materials. When the substrate of an article has a resin on its surface, the water / oil repellent agent of the present invention can be used as a water / oil repellent for resins. By forming a coated film on the surface of the article, the water / oil repellent agent of the present invention can also be used as an antifouling coating material, a protective agent for exterior walls, a release agent for release paper, a mold release agent, and the like. In particular, it can be effectively used as a separator for articles containing silicone-based adhesives. In these applications, the water / oil repellent agent of the present invention can be used as a transparent coating agent as is, or a pigment or the like can be added.

[0053] The method for producing the article of the present invention is not particularly limited, and examples of methods that can be used for applying the water and oil repellent of the present invention to the substrate of the article include spin coating, dip coating, spraying, roll coating, meniscus coating, and screen printing.

[0054] The water- and oil-repellent agent of the present invention can be easily applied to a substrate, such as glass, fiber, or porous membrane, and then the solvent is dried to form a coating on the substrate surface. Specifically, drying is preferably performed at room temperature (25°C ± 10°C) for 30 minutes to 24 hours. To accelerate drying, the substrate may be heated, for example, at 40 to 150°C for 30 seconds to 24 hours, within a range that does not affect the substrate. This coating exhibits excellent water- and oil-repellent properties due to the presence of fluorine atoms in the polymer of component (A). Therefore, the water- and oil-repellent agent of the present invention can be used as a coating agent to form a water- and oil-repellent coating on substrates, such as glass, fiber, and porous membrane, particularly fiber and porous membrane.

[0055] Among the substrates used in the article of the present invention, fibrous substrates can be in the form of, for example, fibers, threads, cloth, etc. Examples of fibers constituting the fibrous substrate include glass fibers, carbon fibers, aramid fibers, polyethylene fibers, polytetrafluoroethylene (PTFE) fibers, Zylon fibers, boron fibers, basalt fibers, metal fibers, polyamide fibers, silicon carbide fibers, polyester fibers, ceramic fibers, alumina fibers, mineral fibers, rock fibers, slag fibers, polyoxymethylene fibers, aromatic polyamide fibers, polyparaphenylene benzobisoxazole fibers, plant fibers, cellulose fibers, and lignin fibers. These fibers may be used alone or in combination of two or more.

[0056] Among the substrates used in the article of the present invention, examples of porous membrane substrates include nonwoven fabrics, perforated membranes, microporous membranes, and porous bodies. Materials constituting the porous membrane substrate include resins such as polytetrafluoroethylene (PTFE), ceramics, metals, etc., and polytetrafluoroethylene (PTFE) is preferred.

[0057] Examples of the article of the present invention include in-vehicle products, textile products, nonwoven fabrics, and filtering materials used in the presence of organic solvent liquids or their vapors.

[0058] As an index of water repellency in the article of the present invention, the contact angle with water (water contact angle) of a coating formed by applying the water / oil repellent of the present invention to a glass plate at a temperature of 25°C and a relative humidity of 40% is preferably 115° or more, more preferably 120° or more. In the present invention, the contact angle with water is a value measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) under conditions of a 2 μL droplet and a relative humidity of 50%.

[0059] Furthermore, as an index of oil repellency in the article of the present invention, the contact angle with hexadecane (hexadecane (HD) contact angle) of a coating formed by applying the water and oil repellent of the present invention to a glass plate at a temperature of 25°C and a relative humidity of 40% is preferably 75° or more, more preferably 78° or more. In the present invention, the contact angle with hexadecane is a value measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) under conditions of a 2 μL droplet and a relative humidity of 50%. [Example]

[0060] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. (PFHxA-related substance content) A known amount of PFHxA-related substances was added to a monomer-containing composition containing the polyfluoroalkylvinyl compound prepared in the examples as a monomer, and to a polymer-containing composition prepared using the same. The sample solution was then subjected to a gas chromatograph-tandem mass spectrometer (GC-MS / MS) to measure the content of PFHxA-related substances. The equipment used is shown below. Measurements were performed with reference to "BS EN 17681-1:2022," "BS EN 17681-2:2022," and "CEN / TS 15968:2010." The lower limit of quantitation was 50 ppb. [Equipment used] Gas chromatograph: Agilent Technologies 7890B Tandem mass spectrometer: Agilent Technologies 7010B

[0061] (molecular weight) The weight average molecular weight (Mw) of the polymer was measured by high performance liquid chromatography. The instruments used and the measurement conditions are shown below. [Equipment used] Liquid transfer pump: Hitachi L-7100 Column oven: Hitachi L-7300 Detector: Eurosep Instruments DDL-31 (Evaporative Light Scattering Detector) [Column conditions] Column: Tosoh TSK-GEL MultiporeHxL x 2 Solvent [mobile phase]: Asahi Glass AK-225 for general industrial use Column temperature: 35℃ Liquid delivery speed: 1.0 ml / min [Detection conditions] Detection temperature: 45℃ PM Gain: 450 N2 gas pressure: 1.5 bar

[0062] [Example 1] (i) Molecular distillation of polyfluoroalkyl vinyl compounds (monomers) The following formula (1) [ka] 200 ppm of 4-methoxyphenol was added to 100 g of a polyfluoroalkyl vinyl compound represented by the formula: 3) was subjected to molecular distillation at a reduced pressure of 55 Pa, 85°C, a feed rate of 3.5 g / min, and a condenser temperature of 25°C to remove low-boiling components, yielding 80.1 g of a purified polyfluoroalkylvinyl compound. Table 1 shows the contents of PFHxA-related substances relative to the total amount of polyfluoroalkylvinyl monomer and PFHxA-related substances before and after molecular distillation. (ii) Polymerization of polyfluoroalkyl vinyl compounds (monomers) A 300 ml four-neck flask equipped with a thermometer, an inert gas inlet, a reflux condenser, and a stirrer was charged with 90 parts by mass of the polyfluoroalkyl vinyl compound obtained in step (i) above, 210 parts by mass of Novec HFE-7300 (manufactured by 3M) as a partially fluorinated solvent, and 0.5 parts by mass of Perbutyl O (organic peroxide polymerization catalyst, product name manufactured by NOF Corporation) as a radical reaction initiator. The mixture was reacted at 65 to 75 ° C for 5 hours while passing nitrogen gas through the mixture, and then aged at the same temperature for 15 hours to prepare a solution (mother liquor) of a polymer (weight average molecular weight (Mw): 210,000) containing the polyfluoroalkyl vinyl compound obtained in step (i) as 100% by mass of the monomer component. (iii) Coating of polyfluoroalkyl vinyl polymer-containing composition The mother liquor obtained in step (ii) above was diluted with Novec HFE-7300 to a solids content of 1% by mass, and the diluted solution was then dip-coated onto a glass plate as a substrate. The dip coating was performed by immersing the plate in water for 10 seconds and then withdrawing it at a rate of 150 mm / min. The film thickness after drying was 0.05 μm. After drying, the plate was heat-treated at 150°C for 30 seconds, and the contact angles of the glass plate with pure water and hexadecane were measured using a contact angle meter (Model A3, manufactured by Kyowa Interface Science Co., Ltd.). The contact angles were 120° with pure water and 75° with hexadecane.

[0063] [Reference example 1] The polyfluoroalkyl vinyl compound (i) is reacted with a compound represented by the following formula (2): [ka] A solution (mother liquor) of a polymer (weight average molecular weight (Mw): 201,000) containing a polyfluoroalkylvinyl compound as 100% by mass of the monomer component was prepared in the same manner as in (i) and (ii) of Example 1, except that the polyfluoroalkylvinyl compound was changed to a polyfluoroalkylvinyl compound represented by the formula:

[0043] . Furthermore, the following operations were carried out in the same manner as in (iii) of Example 1. A diluted solution was prepared from the mother liquor, and this diluted solution was dip-coated onto a glass plate as a substrate. After drying and heat treatment, the contact angles of this glass plate with pure water and hexadecane were measured. As a result, the contact angles were 120° with pure water and 75° with hexadecane.

[0064] [Table 1]

Claims

1. (A) a compound represented by the following formula (I): 【Chemistry 1】 (wherein R is a hydrogen atom or a methyl group, n is a number from 1 to 6, a is a number from 1 to 4, b is a number from 0 to 3, and c is a number from 1 to 3), (B) A polymer-containing composition in which the content of PFHxA-related substances, when there are two or more types, is 1000 ppb or less for each of the contents of each of the substances relative to the total amount of components (A) and (B).

2. The component (B) is represented by the following formula (IIa) or (IIb): 【Chemistry 2】 (In the formula, X 1 is a monovalent organic group.) 【Transformation 3】 (In the formula, X 2 represents a fluorine atom, —C(═O)OH, —C(═O)OY (Y is a monovalent organic group), and —CF 2 is a monovalent organic group excluding Y (Y is a monovalent organic group). The polymer-containing composition according to claim 1, wherein the polymer-containing composition is represented by the formula:

3. 3. The polymer-containing composition according to claim 2, wherein component (B) is at least one selected from the group consisting of 2-(perfluorohexyl)ethyl iodide (CAS Registry Number: 2043-57-4), 2-(perfluorohexyl)ethanol (CAS Registry Number: 647-42-7), 2-(perfluorohexyl)ethyl acrylate (CAS Registry Number: 17527-29-6), and 2-(perfluorohexyl)ethyl methacrylate (CAS Registry Number: 2144-53-8).

4. The polymer-containing composition according to claim 1, wherein the polymer-containing composition contains a fluorine-containing solvent.

5. The polymer-containing composition of claim 1 , wherein the polymer-containing composition does not contain an adsorbent.

6. A water and oil repellent comprising the polymer-containing composition according to any one of claims 1 to 5.

7. An article having a coating of the water and oil repellent agent according to claim 6 on its surface.

8. The article according to claim 7, which has a substrate having a coating of the water and oil repellent agent applied to a surface thereof, and the substrate is a fiber.

9. A method for producing the polymer-containing composition according to claim 1, a purification step of purifying a monomer-containing composition containing the polyfluoroalkylvinyl compound represented by formula (I) and the component (B) so that the content of each of the components (B), when there are two or more components, is 1000 ppb or less relative to the total amount of the polyfluoroalkylvinyl compound represented by formula (I) and the component (B); and A method for producing a polymer-containing composition, comprising a polymerization step of subjecting the monomer-containing composition after the purification step to a polymerization reaction in a solvent to obtain a polymer-containing composition.

10. The component (B) is represented by the following formula (IIa) or (IIb): 【Chemistry 4】 (In the formula, X 1 is a monovalent organic group.) 【Transformation 5】 (In the formula, X 2 is a monovalent organic group, provided that it does not include a fluorine atom, —C(═O)OH, —C(═O)OY (Y is a monovalent organic group), or —CF 2 Y (Y is a monovalent organic group) The method for producing a polymer-containing composition according to claim 9, wherein the polymer-containing composition is represented by the formula:

11. The method for producing a polymer-containing composition according to claim 10, wherein component (B) is at least one selected from the group consisting of 2-(perfluorohexyl)ethyl iodide (CAS Registry Number: 2043-57-4), 2-(perfluorohexyl)ethanol (CAS Registry Number: 647-42-7), 2-(perfluorohexyl)ethyl acrylate (CAS Registry Number: 17527-29-6), and 2-(perfluorohexyl)ethyl methacrylate (CAS Registry Number: 2144-53-8).

12. The method for producing a polymer-containing composition according to any one of claims 9 to 11, wherein the purification is carried out by molecular distillation.

13. The method for producing a polymer-containing composition according to claim 12, wherein the temperature of the molecular distillation is 200°C or less.

14. The method for producing a polymer-containing composition according to claim 12, wherein the degree of vacuum in the molecular distillation is 150 Pa or less.

15. The method for producing a polymer-containing composition according to claim 12, wherein the molecular distillation is carried out by adding 0.01 to 1000 ppm of a polymerization inhibitor to 100 g of the polyfluoroalkylvinyl compound represented by the formula (I).

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