Surface treatment agent and method for producing same, article and method for producing same, compound, and polymer

Abstract

The present disclosure relates to a surface treatment agent comprising a polymer having a unit derived from a compound represented by formula (1). In the formula, T is a monovalent polymerizable group, A is a (1+m)-valent linking group containing neither a fluorine atom nor an aromatic ring, Rf is a perfluoroalkyl group having 1-6 carbon atoms, and m is an integer of 1 or more.　(1): T-A-(ORf)m

Description

Surface treatment agents, methods for producing the same, articles, methods for producing the same, compounds and polymers

[0001] This disclosure relates to surface treatment agents, methods for producing the same, articles, methods for producing the same, compounds, and polymers. This application claims priority to Japanese Patent Application No. 2024-185346, filed in Japan on October 21, 2024, the contents of which are incorporated herein by reference.

[0002] Conventionally, various materials have been subjected to water-repellent and oil-repellent properties. One method for imparting these properties is to treat the surface to be treated with a surface treatment agent containing a fluorine-containing polymer. A known fluorine-containing polymer used in such applications is a copolymer of tetrafluoroethylene (TFE) and perfluoro-(2,2-dimethyl-1,3-dioxole) (PDD) (Teflon® AF) (Patent Document 1).

[0003] Japanese Patent Application Publication No. 5-320255

[0004] However, according to the present disclosers' studies, treating a separation membrane with a surface treatment agent containing the copolymer tends to impair the permeability of the separation membrane. Furthermore, the copolymer dissolves only in fluorine solvents, which raise concerns about environmental impact.

[0005] This disclosure provides a surface treatment agent comprising a polymer soluble in a non-fluorine solvent that yields a separation membrane with excellent permeability, and a method for producing the same; an article using the surface treatment agent and a method for producing the same; a novel polymer soluble in a non-fluorine solvent and useful as a component of the surface treatment agent; and a novel compound useful as a monomer for forming the polymer.

[0006] This disclosure provides a surface treatment agent having the following configurations [1] to

[24] , a method for producing the same, an article, a method for producing the same, a compound and a polymer. [1] A surface treatment agent comprising a polymer having a unit based on a compound represented by the following formula 1. T-A-(OR ｆ ) ｍ ... (1) However, T is a monovalent polymerizable group, A is a (1+m)valent linking group that does not have a fluorine atom or an aromatic ring, and R ｆis a perfluoroalkyl group having 1 to 6 carbon atoms, and m is an integer of 1 or more. [2] The surface treatment agent of [1] for a separation membrane. [3] R in the formula 1 ｆ The surface treatment agent of [1] or [2] wherein is a trifluoromethyl group. [4] The surface treatment agent of any one of [1] to [3] wherein A in the formula 1 is a saturated hydrocarbon group having (1 + m) valences. [5] The surface treatment agent of any one of [1] to [4] wherein T in the formula 1 is a group having a polymerizable unsaturated bond, a group containing a cyclic ether structure, or a reactive silyl group. [6] The surface treatment agent of any one of [1] to [5] wherein T in the formula 1 is a (meth)acryloyloxy group or a (meth)acrylamide group. [7] The surface treatment agent of any one of [1] to [6] wherein the content of the unit based on the compound in the polymer is 5% by mass or more based on all the units constituting the polymer. [8] The surface treatment agent of any one of [1] to [7] wherein the mass average molecular weight of the polymer is 5,000 to 800,000. [9] The surface treatment agent of any one of [1] to [8] further containing a liquid medium.

[10] The surface treatment agent of [9] wherein the liquid medium contains a solvent not containing a fluorine atom.

[11] The surface treatment agent of any one of [1] to

[10] wherein the content of the polymer is 0.5 to 30% by mass based on the total mass of the surface treatment agent.

[12] A method for producing a surface treatment agent, comprising polymerizing a monomer component containing a compound represented by the following formula 1 in the presence of a polymerization initiator. T-A-(OR ｆ ) ｍ ...(1) However, T is a monovalent polymerizable group, A is a (1 + m)-valent linking group having no fluorine atom and no aromatic ring, R ｆ is a perfluoroalkyl group having 1 to 6 carbon atoms, and m is an integer of 1 or more.

[13] An article comprising a substrate and a polymer having a unit based on a compound represented by the following formula 1 adhered to the surface of the substrate. T-A-(OR ｆ ) ｍ ...(1) However, T is a monovalent polymerizable group, A is a (1 + m)-valent linking group having no fluorine atom and no aromatic ring, R ｆis a perfluoroalkyl group having 1 to 6 carbon atoms, and m is an integer of 1 or more.

[14] The article of

[13] , which is a separation membrane, wherein the substrate is a porous substrate.

[15] The amount of polymer attached is 1 × 10 per unit area of ​​the substrate. －６ ~5 x 10 －３ g / cm ２ The article according to

[13] or

[14] , wherein the base material comprises at least one selected from the group consisting of polytetrafluoroethylene, polyester, polyphenylene sulfide, polyolefin, polystyrene, polyvinyl chloride, polyamide, polyimide, glass, metal, metal oxide, carbon, and cellulose.

[17] A method for producing an article, wherein the surface of the base material is treated with any of the surface treatment agents according to [1] to

[11] .

[18] A method for producing an article according to

[17] , wherein the article is a separation membrane and the base material is a porous base material.

[19] A method for producing an article according to

[17] , wherein the base material comprises at least one selected from the group consisting of polytetrafluoroethylene, polyester, polyphenylene sulfide, polyolefin, polystyrene, polyvinyl chloride, polyamide, polyimide, glass, metal, metal oxide, carbon, and cellulose.

[20] A method for producing the article according to

[18] , wherein the base material comprises at least one selected from the group consisting of polytetrafluoroethylene, polyester, polyphenylene sulfide, polyolefin, polystyrene, polyvinyl chloride, polyamide, polyimide, glass, metal, metal oxide, carbon, and cellulose.

[21] A compound represented by the following formula 1A. T ２ -A-(OCF) ３ ) ｍ ... (1A) However, T ２ is a (meth)acryloyloxy group or a (meth)acrylamide group, where A is a (1+m) valence linking group that does not have a fluorine atom or an aromatic ring, and m is an integer of 1 or more.

[22] A polymer having units based on the compound represented by the following formula 1A. T ２ -A-(OCF) ３ ) ｍ ... (1A) However, T ２a is a (meth)acryloyloxy group or a (meth)acrylamide group, where A is a (1+m) valence linking group that does not have a fluorine atom or an aromatic ring, and m is an integer of 1 or more.

[23] The polymer of

[22] wherein the content of units based on the compound is 5% by mass or more with respect to the total units constituting the polymer.

[24] The polymer of

[22] or

[23] wherein the mass average molecular weight is 5,000 to 800,000.

[0007] The surface treatment agent of this disclosure contains a polymer soluble in a non-fluorine solvent and provides a separation membrane with excellent permeability. The polymer of this disclosure is soluble in a non-fluorine solvent and is useful as a component of the surface treatment agent of this disclosure.

[0008] The meanings and definitions of terms used in this specification are as follows: A compound-based unit is an atomic group directly formed by the polymerization of one monomeric compound molecule. "Fluoroalkyl group" means a group in which one or more hydrogen atoms of the alkyl group are replaced with fluorine atoms. "Polyfluoroalkyl group" means a group in which two or more hydrogen atoms of the alkyl group are replaced with fluorine atoms. "Perfluoroalkyl group" means a group in which all of the hydrogen atoms of the alkyl group are replaced with fluorine atoms. "(meth)acryloyloxy group" is a general term for acryloyloxy group and methacryloyloxy group. The same applies to "(meth)acrylamide group", "(meth)acrylate", "(meth)acrylamide", and "(meth)acrylic acid". The mass-average molecular weight (hereinafter also referred to as "Mw") of a polymer is the polystyrene-equivalent molecular weight obtained by measuring it by gel permeation chromatography (hereinafter also referred to as "GPC") using a calibration curve prepared using a standard polystyrene sample. The solid content concentration is calculated by (solid content mass / sample mass) × 100, where the sample mass before heating is the sample mass and the solid content mass is the mass after drying the sample in a convection dryer at 120°C for 4 hours. In this specification, solvents that do not contain fluorine atoms are also referred to as "non-fluorine solvents." Solvents that contain fluorine atoms are also referred to as "fluorine-containing solvents." In this specification, a compound represented by formula (X) is also referred to as compound X. A group represented by formula (X) is also referred to as group X. In this specification, the "~" indicating a numerical range means that the values ​​written before and after it are included as the lower and upper limits, respectively.

[0009] [Surface Treatment Agent] The surface treatment agent of this disclosure (hereinafter also referred to as "this treatment agent") comprises a polymer having units based on compound 1 described later (hereinafter also referred to as "polymer I"). This treatment agent may further contain a liquid medium. This treatment agent may further contain other components other than polymer I and the liquid medium.

[0010] (Compound 1) Compound 1 is a compound represented by the following formula 1. T-A-(OR ｆ ) ｍ... (1) However, T is a monovalent polymerizable group. A is a (1+m)valent linking group that does not have a fluorine atom or an aromatic ring. R ｆ m is a perfluoroalkyl group having 1 to 6 carbon atoms. m is an integer greater than or equal to 1.

[0011] <T> T is a monovalent polymerizable group. There are no particular restrictions on T. For example, T may be a radical polymerizable group, a cationic polymerizable group, or an anionic polymerizable group.

[0012] T may be, for example, a group having a polymerizable unsaturated bond, a group containing a cyclic ether structure, or a reactive silyl group. Examples of polymerizable unsaturated bonds include polymerizable carbon-carbon double bonds and polymerizable carbon-carbon triple bonds. Examples of groups having a polymerizable carbon-carbon double bond include group 2, a vinyloxy group, an allyloxy group, a fumarate group, a maleimide group, and group 3. Among these, group 2 is preferred.

[0013] ＊Ａ -R ２ -C(=O)-CR １ =CH ２ ... (2) However, R １ R is a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 12 carbon atoms. ２ is a single bond, oxygen atom, or NR ３ It is a divalent group represented by . ＊Ａ This is a bonding relationship with A. ３ This is a hydrogen atom, or a linear or branched alkyl group having 1 to 12 carbon atoms.

[0014] R １ Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. １ R is preferably a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. ２ is an oxygen atom, or NR ３ A divalent group represented by R is preferred. ３ ​The first group is preferably a hydrogen atom or a linear alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. The second group is preferably a (meth)acryloyloxy group or a (meth)acrylamide group.

[0015] However, R １０１ ~R １０５ One of these is a bond with A, and the others are, independently, a hydrogen atom, a halogen atom, or a C1-C4 halogenated alkyl group.

[0016] Examples of cyclic ether structure-containing groups include epoxy group-containing groups and oxetanyl group-containing groups.

[0017] Group 4 is an example of a reactive silyl group.

[0018] ＊Ａ -SiR ４ ３－ａ X ａ ... (4) However, X is a hydroxyl group, a halogen atom, or a hydrolyzable group. R ４ X is a monovalent organic group having 1 to 20 carbon atoms, and is not a hydrolyzable organic group. a is an integer between 2 and 3. Multiple Xs may be the same or different. ＊Ａ - represents a combination with A.

[0019] Examples of hydrolyzable groups of X include halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, sulfanyl groups, and alkenyloxy groups. A chlorine atom is preferred as the halogen atom. An alkoxy group is preferred as the hydrolyzable group due to its mild hydrolysis and ease of handling. The alkoxy group is preferably a methoxy group, ethoxy group, or isopropoxy group, with methoxy or ethoxy groups being more preferred. When the alkoxy group is a methoxy or ethoxy group, siloxane bonds are readily formed.

[0020] R ４ ​Preferably, the group is an alkyl group, cycloalkyl group, aryl group, α-chloroalkyl group, or triorganosiloxy group. Among these, linear or branched alkyl groups having 1 to 4 carbon atoms, cyclohexyl group, phenyl group, benzyl group, α-chloromethyl group, trimethylsiloxy group, triethylsiloxy group, or triphenylsiloxy group are preferred.

[0021] Examples of the aforementioned group 4 include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, tris(2-propenyloxy)silyl group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, methyldiisopropoxysilyl group, (α-chloromethyl)dimethoxysilyl group, and (α-chloromethyl)diethoxysilyl group. Among these, trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, and diethoxymethylsilyl group are preferred, and dimethoxymethylsilyl group is more preferred.

[0022] T is a hydroxyl group in formula (4), ＊Ａ , R ４ The range and preferred range of a may be the same as that of formula (4).

[0023] A is a (1+m) valency linking group that does not have a fluorine atom or an aromatic ring. Examples of A include (i) a (1+m) valency saturated hydrocarbon group, (ii) a group in which a bond selected from the group consisting of an ether bond, amide bond, urea bond, urethane bond, sulfide bond, ester bond, and amino bond is inserted between the carbon-carbon bonds of a (1+m) valency saturated hydrocarbon group, or (iii) a group in which one or two hydrogen atoms bonded to the carbon atom of the group in (i) or (ii) above are substituted with a hydroxyl group, a chlorine atom, a bromine atom, or an iodine atom.

[0024] Examples of (1+m) valency saturated hydrocarbon groups include linear saturated hydrocarbon groups, cyclic saturated hydrocarbon groups, and groups consisting of combinations thereof. Linear saturated hydrocarbon groups may be straight or branched. The number of carbon atoms in a linear saturated hydrocarbon group is preferably 1 to 26, and more preferably 2 to 22. Cyclic saturated hydrocarbon groups may be monocyclic or fused. The number of members in the ring structure of a monocyclic group is preferably 3 to 10, and more preferably 4 to 7. In the case of a fused ring, the number of rings constituting the cyclic saturated hydrocarbon group is preferably 2 to 3, and more preferably 2. The number of members in these rings is preferably 3 to 8, and more preferably 5 to 7.

[0025] The (1+m) valent saturated hydrocarbon group is preferably group a1, group a2, or group a3. ＊Ｔ -R ５ - ＊ｆ ... (a1) ＊Ｔ -L １ -CH (-CH ２ - ＊ｆ ) ２ ... (a2) ＊Ｔ -L ２ -C(-CH) ２ - ＊ｆ ) ３ ... (a3) ​​However, R ５ L is a linear alkylene group. １ and L ２ Each of these is independently a methylene group or a single bond. ＊Ｔ - is a bonding with T, - ＊ｆ is OR ｆ This is a combination of R. ５ The number of carbon atoms is preferably 1 to 26, more preferably 2 to 22, and even more preferably 16 to 22. When the number of carbon atoms is below the upper limit, the proportion of fluorine atoms in compound 1 increases, resulting in better oil repellency. When the number of carbon atoms is above the lower limit, particularly 16 or more, crystallinity is exhibited, resulting in better oil repellency.

[0026] <OR ｆ > R ｆ These are perfluoroalkyl groups with 1 to 6 carbon atoms. When the number of carbon atoms is 6 or less, bioaccumulative activity and environmental toxicity are low. ｆThe number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1. Therefore, R ｆ A trifluoromethyl group is particularly preferred.

[0027] <m> m is an integer greater than or equal to 1. m may be 2 or greater. A higher value of m tends to result in better water-repellent and oil-repellent properties. There is no particular upper limit to m. For example, m is 5 or less. The range is preferably 1 to 5, and more preferably 2 to 5.

[0028] Compound 1A is exemplified as a preferred embodiment of Compound 1. Compound 1A is preferred in that it exhibits excellent water repellency and oil repellency. ２ -A-(OCF) ３ ) ｍ ... (1A) However, T ２ is a (meth)acryloyloxy group or a (meth)acrylamide group, and A and m are as described above. In compound 1A, A is preferably a (1+m) valent saturated hydrocarbon group because it has superior solubility in organic solvents and oil repellency.

[0029] Examples of compound 1A include the following:

[0030] However, R is a hydrogen atom or a methyl group, ３ As stated above, n is an integer from 1 to 21.

[0031] Examples of compound 1 other than compound 1A include the following:

[0032]

[0033] Compound 1 can be produced by appropriately combining known methods. For example, it can be produced by reacting compound 11 and compound 12. H-R ２ -A-(OR ｆ ) ｍ ...(11) Cl-C(=O)-CR １ =CH ２ ... (12) However, A, R ｆ , m, R １ , R ２ This is as stated above.

[0034] Compounds 11 and 12 can be commercially available products. As shown in the examples described later, they may also be prepared by appropriately combining known methods. An example of a method for reacting compound 11 and compound 12 is to mix compound 11, compound 12, a liquid medium, and a catalyst, and then stir the mixture. Examples of catalysts include base catalysts such as triethylamine, 2,6-lutidine, and N,N-dimethylaniline. Examples of liquid media include dichloromethane, chloroform, and 1,1,2,2-tetrachloroethane. The reaction temperature is, for example, 0 to 40°C. After the reaction, the liquid medium can be removed, purified, etc., as needed.

[0035] (Polymer) Polymer I has units based on compound 1. Polymer I may have one or more units based on compound 1.

[0036] Polymer I may further have units based on monomers other than compound 1. The other monomers can be copolymerizable with compound 1 and can be appropriately selected from known monomers. Examples of polymerizable groups of the other monomers include groups having polymerizable unsaturated bonds, groups containing cyclic ether structures, and reactive silyl groups. Examples of these groups are the same as those described above. From the viewpoint of improving copolymerizability, monomers having polymerizable groups similar to those of compound 1 are preferred.

[0037] Examples of monomers containing a cyclic ether structure include butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-epoxycyclohexane, benzyl glycidyl ether, 1,7-octadiene diepoxide, glycidyl acrylate, glycidyl methacrylate, cyclopentadiene diepoxide, glycerol triglycidyl ether, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyloxirane, bis(3-ethyl-3-oxetanylmethyl) ether, (3-ethyloxetan-3-yl)methyl methacrylate, and 3-ethyl-3-oxetane methanol. These may be used individually or in combination of two or more.

[0038] Examples of monomers having a reactive silyl group include trimethoxymethylsilane, hexyltrimethoxysilane, trimethoxyphenylsilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyl(diethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-(acryloxy)propyltrimethoxysilane, 3-(acryloxy)propyltriethoxysilane, and methyltrichlorosilane. These can be used individually or in combination of two or more types.

[0039] Examples of monomers having polymerizable unsaturated bonds include (meth)acrylic acid, (meth)acrylates, (meth)acrylamides, unconjugated vinyl monomers, styrenes, and maleimides.

[0040] Examples of (meth)acrylates or (meth)acrylamides include: (meth)acrylamides (unsubstituted); (meth)acrylates or (meth)acrylamides having alkyl groups, such as methyl (meth)acrylate, ethyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl acrylate, etc.; (meth)acrylates or (meth)acrylamides having polar groups inside the compound (other than at the terminals), such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethylene glycol monoacetate mono(meth)acrylate, ethylene glycol di(meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, and the compounds listed below;

[0041]

[0042] Hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1-(acryloyloxy)-3-((meth)acryloyloxy)-2-propanol, and other compounds listed below, including (meth)acrylates or (meth)acrylamides having polar groups at the termini of the compound;

[0043]

[0044] (Meth)acrylates or (meth)acrylamides having aromatic groups such as phenyl (meth)acrylate, benzyl (meth)acrylate, pentafluorobenzyl (meth)acrylate, 2-phenylethyl (meth)acrylate, and furfuryl (meth)acrylate. Of these, (meth)acrylates or (meth)acrylamides having polar groups inside the compound (other than at the ends), particularly the compounds described in paragraph 0041, are preferred in that they contribute to improved water and oil repellency. (Meth)acrylates or (meth)acrylamides having polar groups at the ends of the compound, particularly the compounds described in paragraph 0043, are preferred in that they contribute to improved adhesion to fibers and the like.

[0045] Examples of non-conjugated vinyl monomers include vinyl chloride, trimethylvinylsilane, cyclohexylbutyl vinyl ether, allyl butyl ether, diethylene glycol monovinyl ether, vinyl propionate, vinyl benzoate, vinyl (meth)acrylate, allyl (meth)acrylate, and the following compounds.

[0046]

[0047] Examples of styrenes include styrene, 4-chlorostyrene, pentafluorostyrene, 4-methylstyrene, 4-methoxystyrene, 4-aminostyrene, 4-vinylbenzoic acid, and 4-vinylphenol.

[0048] Examples of maleimides include N-methylmaleimide and N-phenylmaleimide.

[0049] In polymer I, the content of units based on compound 1 is preferably 5% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, particularly preferably 60% by mass or more, most preferably 70% by mass or more, and may be 100% by mass, relative to the total units constituting polymer I. If polymer I contains units other than those based on compound 1, the upper limit of the content of units based on compound 1 is preferably 95% by mass or less, more preferably 90% by mass or less. If polymer I contains units other than those based on compound 1, the range of the content of units based on compound 1 is preferably more than 50% by mass and 95% by mass or less, more preferably 60 to 95% by mass, and particularly preferably 70 to 90% by mass. In polymer I, if the content of units based on compound 1 is above the lower limit, the permeability of the separation membrane treated with this treatment agent is better. In addition, the heat resistance and solubility in liquid media of polymer I are better.

[0050] If polymer I has units based on two or more monomers, the content of each unit is: １ The reaction rates of each monomer can be calculated by H-NMR, gas chromatography, and high-performance liquid chromatography. When polymer I is produced, if the conversion rate of monomers to polymer I is high (e.g., 90% or more), the content of each unit may be calculated based on the amount of monomers charged.

[0051] The Mw of polymer I is preferably 5,000 to 800,000, more preferably 10,000 to 500,000, and even more preferably 20,000 to 300,000. When Mw is above the lower limit, the heat resistance and liquid repellency are better. When Mw is below the upper limit, the viscosity of the polymer I solution is lower, and the permeability of the separation membrane treated with the composition containing the polymer I solution is better.

[0052] If polymer I has a glass transition temperature (hereinafter also referred to as "Tg"), the Tg of polymer I is preferably 10°C or higher, more preferably 20°C or higher, and even more preferably 40°C or higher. A higher Tg is preferable. There is no particular upper limit, but for example, it is 300°C or lower. The Tg of polymer I is preferably 10 to 300°C, more preferably 20 to 300°C, and even more preferably 40 to 300°C. If the Tg is above the lower limit, this treatment agent can also be applied to separation membranes where heat resistance is required. In addition, excellent water-repellent and oil-repellent properties tend to be exhibited at around room temperature (for example, 25°C). Details of the method for measuring Tg are as described in the examples below.

[0053] If polymer I has a melting point (hereinafter also referred to as "Tm"), the melting point of polymer I is preferably 20°C or higher, and more preferably 40°C or higher. A higher Tm is preferable. There is no particular upper limit, but for example, it is 300°C or lower. The Tm of polymer I is preferably 20 to 300°C, and more preferably 40 to 300°C. If Tm is above the lower limit, this treatment agent can also be applied to separation membranes where heat resistance is required. Details of the method for measuring Tm are as described in the examples below.

[0054] The 5% thermal decomposition temperature of polymer I (hereinafter also referred to as "5% Td") is preferably 150°C or higher, more preferably 200°C or higher, even more preferably 250°C or higher, and particularly preferably 300°C or higher. A higher 5% Td is preferable. There is no particular upper limit, but for example, it is 500°C or lower. The 5% Td of polymer I is preferably 150 to 500°C, more preferably 200 to 500°C, even more preferably 250 to 500°C, and particularly preferably 300 to 500°C. If the 5% Td is above the lower limit, this treatment agent can also be applied to separation membranes where heat resistance is required. Details of the method for measuring 5% Td are as described in the examples below.

[0055] The water contact angle of the surface of the coating film formed by coating a glass substrate with a solution of polymer I dissolved in a solvent and drying it is preferably 90° or higher, more preferably 95° or higher, and even more preferably 100° or higher. If the water contact angle is above the lower limit, the separation film treated with this treatment agent can be applied to applications where water repellency and water resistance are required. Details of the method for measuring the water contact angle are described in the examples below.

[0056] The hexadecane contact angle of the coating film formed by coating a glass substrate with a solution of polymer I dissolved in a solvent and drying it is preferably 35° or higher, more preferably 40° or higher, even more preferably 55° or higher, particularly preferably 60° or higher, and most preferably 65° or higher. If the hexadecane contact angle is above the lower limit, the separation film treated with this treatment agent can be applied to applications where oil repellency and oil resistance are required. Details of the method for measuring the hexadecane contact angle are described in the examples below.

[0057] Polymer I can be produced by polymerizing monomer components containing compound (1). Further details will be explained later. Polymer I may be produced using one type alone or in combination of two or more types.

[0058] (Liquid medium) When this treatment agent contains a liquid medium, it is easier to treat the porous substrate of the separation membrane with this treatment agent. The liquid medium can be appropriately selected from known liquid media. The liquid medium is preferably one that dissolves or disperses polymer I, and more preferably one that dissolves polymer I.

[0059] Examples of liquid media include non-fluorinated solvents (solvents that do not contain fluorine atoms) and fluorinated solvents (solvents that contain fluorine atoms).

[0060] Examples of non-fluorinated solvents include hydrocarbon solvents, ketone solvents, alcohol solvents, ester solvents, amide solvents, and ether solvents.

[0061] Examples of hydrocarbon solvents include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene. Examples of ketone solvents include methyl ethyl ketone (hereinafter also referred to as "MEK"), methyl isobutyl ketone, and cyclohexanone. Examples of alcohol solvents include ethanol, 1-propanol, 2-propanol, 1-butanol, and ethylene glycol.

[0062] Examples of ester solvents include methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, ethyl-3-ethoxypropionate, cyclohexanol acetate, γ-butyrolactone, 3-methyl-3-methoxybutyl acetate, and glycerin triacetate.

[0063] Examples of amide solvents include dimethylacetamide, 3-methoxy-dimethylpropanamide, 3-butoxy-dimethylpropanamide, and methylpyrrolidone. Examples of ether solvents include 1,4-dioxane, diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dibutyl ether, and diethylene glycol methyl ethyl ether.

[0064] Examples of fluorine-containing solvents include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols, and hydrofluoroolefins (HFO). Examples of fluorinated alkanes include dichloropentafluoropropane, 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorola (registered trademark) H manufactured by Nippon Zeon Co., Ltd.), C ６ F １３ H (e.g., Asahiklin (registered trademark) AC-2000 manufactured by AGC), C ６ F １３ C ２ H ５ (e.g., Asahiklin (registered trademark) AC-6000 manufactured by AGC), C ２ F ５ CHFCHFCF ３ (e.g., Vertrel (registered trademark) XF manufactured by Chemours). Examples of fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. Examples of fluoroalkyl ethers include CF ３ CH ２ OCF ２ CF ２ H (e.g., Asahiklin (registered trademark) AE-3000 manufactured by AGC), C ４ F ９ OCH ３ (e.g., Novec (registered trademark) 7100 manufactured by Sumitomo 3M Limited), C４ F ９ OC ２ H ５ (For example, Novec® 7200 manufactured by Sumitomo 3M Limited), C ２ F ５ CF(OCH) ３ ) C ３ F ７ (For example, Novec® 7300 manufactured by Sumitomo 3M Limited is an example.) Examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoro-2-propanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 1H,1H,7H-dodecafluoro-1-heptanol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol, and 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1-nonanol. Examples of HFOs include 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd) (for example, Amorea® AS-300 manufactured by AGC Corporation) and Opteon® SF01, SF05, SF10, SF30, SF33, SF70, SF79, and SF80 manufactured by Chemours Corporation.

[0065] The liquid medium may be used alone or in combination of two or more types. Non-fluorinated solvents tend to have a lower global warming potential than fluorinated solvents. Therefore, it is preferable that the liquid medium contains a non-fluorinated solvent. The content of the non-fluorinated solvent is preferably 50% by mass or more, more preferably 80% by mass or more, and may be 100% by mass, based on the total mass of the liquid medium.

[0066] (Other ingredients) Examples of other ingredients include antioxidants and dyes. Other ingredients may be used individually or in combination of two or more.

[0067] (Content of each component) The content of polymer I in this treatment agent may be, for example, 0.5% by mass or more, 2% by mass or more, 10% by mass or more, or 100% by mass, relative to the total mass of this treatment agent. When the content of polymer I is above the lower limit, the water-repellent and oil-repellent properties of the separation membrane treated with this treatment agent are better. When this treatment agent contains components other than polymer I, such as a liquid medium, the content of polymer I is preferably 0.5 to 30% by mass, more preferably 0.5 to 10% by mass, and even more preferably 0.5 to 2% by mass, relative to the total mass of this treatment agent. When the content of polymer I is below the upper limit, the viscosity of this treatment agent is lower, and the permeability of the separation membrane treated with this treatment agent is better.

[0068] The content of polymer I is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 50% by mass or more, and may also be 100% by mass, based on the total solid content of the treatment agent. When the content of polymer I is above the lower limit, the water-repellent and oil-repellent properties of the separation membrane treated with the treatment agent are better.

[0069] If the treatment agent contains a liquid medium, the amount of liquid medium can be set according to the desired solid content concentration of the treatment agent. The solid content concentration of the treatment agent immediately after manufacture is preferably 10 to 80% by mass, and more preferably 20 to 80% by mass, based on the total mass of the treatment agent. When the treatment agent is used to treat a porous substrate of a separation membrane, the solid content concentration of the treatment agent is preferably 0.5 to 30% by mass, and more preferably 2 to 30% by mass, based on the total mass of the treatment agent.

[0070] [Method for Manufacturing Surface Treatment Agent] This treatment agent can be manufactured, for example, by polymerizing a monomer component containing compound 1. The monomer component may contain monomers other than compound 1. The composition (type and amount) of the monomer component should be appropriately set to satisfy the composition of polymer I to be manufactured. Typically, the content (mass%) of compound 1 relative to the total monomers constituting the monomer component is the same as the content (mass%) of units based on compound 1 relative to the total units constituting polymer I. The same applies to other monomers.

[0071] (Polymerization Initiator) The monomer components are preferably polymerized in the presence of a polymerization initiator. There are no particular restrictions on the polymerization initiator, and it can be appropriately selected depending on the type of polymerizable group of the monomer component. Examples of polymerization initiators include: organic peroxides, inorganic peroxides, azo compounds, etc., used in radical polymerization; organic acids, inorganic acids, Lewis acids, and thermal cationic polymerization initiators or photocatalytic cationic polymerization initiators, etc., used in cationic polymerization; and organometallic compounds and photoanionic polymerization initiators, used in anionic polymerization, that generate organic bases in the polymerization system. These may be used individually or in combination of two or more.

[0072] Examples of organic peroxides include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, and t-butyl-α-cumyl peroxide. These may be used individually or in combination of two or more. Examples of inorganic peroxides include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and percarbonates. These may be used individually or in combination of two or more. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitride), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyrate dimethyl, and 2,2'-azobis(2-amidinopropane) dihydrochloride. These can be used individually or in combination of two or more. Furthermore, commercially available azo compounds such as V-59 and V-65 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) can also be used.

[0073] Examples of organic acids include trifluoroacetic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, tetrafluoroboric acid, fluoroantimonic acid, and hexafluorophosphate. Examples of Lewis acids include trichloroaluminum, ethylaluminum dichloride, and ethylaluminum sesquichloride. An example of a thermal cationic polymerization initiator is benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate. Examples of photocatalytic cationic polymerization initiators include commercially available products such as WPI-113, WPI-116, and WPI-170 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries). There are no particular restrictions on organometallic compounds; for example, n-butyllithium, sec-butyllithium, t-butyllithium, diethylzinc, and triethylaluminum are examples. There are no particular restrictions on the photoanionic polymerization initiator; for example, commercially available products such as WPBG-266, WPBG-300, and WPGB-345 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are examples.

[0074] The amount of polymerization initiator added is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total monomer components. The polymerization temperature is preferably 20 to 150°C, and more preferably 40 to 90°C. The polymerization time varies depending on the reaction temperature, but is preferably 1 to 144 hours, and more preferably 3 to 86 hours. Polymerization is preferably carried out in an inert atmosphere such as nitrogen.

[0075] (Molecular weight modifiers) When polymerizing monomer components, molecular weight modifiers may be used. Preferred molecular weight modifiers include aromatic compounds, mercapto alcohols, mercaptocarboxylic acids, and alkyl mercaptans, with mercaptocarboxylic acids or alkyl mercaptans being more preferred. Examples of molecular weight modifiers include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, and α-methylstyrene dimer (CH4). ２ = C(Ph)CH ２ C (CH ３ ) ２Examples include Ph, where Ph is a phenyl group. The amount of molecular weight adjuster added is preferably 0 to 5 parts by mass, and more preferably 0 to 2 parts by mass, per 100 parts by mass of the total monomer components.

[0076] (Chain Transfer Agents) When polymerizing monomer components, chain transfer agents that enable living radical polymerization may be used for further molecular weight control. Reversible addition-cleavage chain transfer agents are preferred. Examples of reversible addition-cleavage chain transfer agents include cyanomethyl dodecyltrithiocarbonate, 2-cyano-2-propylbenzodithioate, 2-(dodecylthiocarbonothiothio)-2-methylpropanoic acid, and cyanomethyl methyl(phenyl)carbamodithioate. In particular, when monomers having two or more polymerizable groups in one molecule are used for polymerization, adding such chain transfer agents is preferable because it can suppress gelation and precipitation of polymer I. The amount of chain transfer agent added is preferably 0 to 2 parts by mass, and more preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total monomer components.

[0077] (Catalyst) A catalyst may be used to obtain polymer I. Examples of catalysts include tin compounds such as dibutyltin dilaurate (dibutyltin dilaurate (DBTDL)); and basic catalysts such as 1,4-diazabicyclo[2.2.2]octane (DABCO). These may be used individually or in combination of two or more. The amount of catalyst added is preferably 0 to 2 parts by mass, and more preferably 0 to 0.5 parts by mass, per 100 parts by mass of the total monomer components.

[0078] (Polymerization) Examples of polymerization methods include solution polymerization, emulsion polymerization, and bulk polymerization. Among these, solution polymerization and emulsion polymerization are preferred, and solution polymerization is more preferred. Solution polymerization is advantageous because it polymerizes monomer components without using emulsifiers, making it easy to control the composition and less likely to introduce impurities.

[0079] Organic solvents are preferred as the medium used in the solution polymerization method. Examples of organic solvents include hydrocarbon solvents, alcohol solvents, ketone solvents, ether solvents, and ester solvents, and the examples of each solvent are the same as those for the liquid medium in the surface treatment agent for separation membranes described above. One organic solvent may be used alone, or two or more may be used in combination.

[0080] In emulsion polymerization, for example, monomer components are polymerized in an emulsion containing monomer components, an aqueous medium, an emulsifier, and a polymerization initiator. Examples of the aqueous medium include water or a mixture of water and a water-soluble organic solvent. The water-soluble organic solvent is an organic solvent that is miscible with water in any proportion. Preferably, the water-soluble organic solvent is at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, and aprotic polar solvents. When the aqueous medium contains a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of water.

[0081] Emulsifiers are surfactants that have both hydrophilic and hydrophobic parts. Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers. Non-fluorinated emulsifiers that do not contain fluorine atoms are preferred. As for emulsifiers, the same emulsifiers as those described later can be used. As for emulsifiers, from the standpoint of excellent dispersion stability of the coating composition, the use of a nonionic emulsifier alone, a combination of a nonionic emulsifier and a cationic or amphoteric emulsifier, or the use of an anionic emulsifier alone is preferred, and the combination of a nonionic emulsifier and a cationic emulsifier is more preferred.

[0082] When the polymerizable reactive group of the monomer component is a group having a polymerizable unsaturated bond, polymer I can be obtained by polymerizing the monomer component in the presence of a polymerization initiator used in radical polymerization or a polymerization initiator used in anionic polymerization. In particular, it is preferable to use a polymerization initiator used in radical polymerization, and azo compounds are more preferable.

[0083] When the polymerizable reactive group of the monomer component is a reactive silyl group, polymer I can be obtained by polymerizing the monomer component in the presence of a polymerization initiator used in cationic polymerization or an anionic polymerization. In particular, it is preferable to use a polymerization initiator used in cationic polymerization. Organic acids, inorganic acids, and Lewis acids, which are polymerization initiators used in cationic polymerization, function as catalysts for hydrolysis reactions. Furthermore, the polymerization initiator is not limited to organic acids, inorganic acids, and Lewis acids, but is not limited to any agent that catalyzes hydrolysis; for example, inorganic bases and organic bases may be used. For example, when X of the reactive silyl group is a hydrolyzable group, the hydrolyzable group of the reactive silyl group is hydrolyzed and converted to a hydroxyl group, and the hydroxyl group undergoes dehydration condensation to form a siloxane bond, and polymerization proceeds.

[0084] The product obtained by polymerizing monomer components contains polymer I. The product may be a solution or dispersion containing polymer I and a polymerization medium. The product may be used as is as the treatment agent, or it may be used as the treatment agent after one or more of the following treatments are performed: removal of the polymerization medium, addition of a liquid medium, addition of other components, or filtration.

[0085] [Article] The article of this disclosure comprises a substrate and polymer I. Polymer I is attached to the surface of the substrate. Polymer I may be one type or more of two types. Other components may be attached to the surface of the substrate. The other components may be one type or more of two types.

[0086] The amount of polymer I attached is 1 × 10⁻⁶ per unit area of ​​the substrate. －６ g / cm ２ The above is preferable, 2 x 10 －６ g / cm ２ The above is more preferable, and also 5 × 10 －３ g / cm ２ The following is preferable: 2.5 × 10 －３ g / cm ２The following is more preferable. The lower limit and upper limit can be combined as appropriate. If the amount of polymer I attached is greater than or equal to the lower limit, the water-repellent and oil-repellent properties of the article are better. If the amount of polymer I attached is less than or equal to the upper limit, when the article is a separation membrane and the substrate is a porous substrate, the air permeability of the porous substrate is less likely to be impaired by polymer I, and the air permeability of the separation membrane is better. The amount of polymer I attached can be measured using a precision electronic balance.

[0087] The base material may be an article or a known base material thereof. There are no particular restrictions on the material of the base material, and examples include resins, glass, metals, metal oxides, carbon, and cellulose. Examples of resins include polytetrafluoroethylene (hereinafter also referred to as "PTFE"), polyester (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate), polyphenylene sulfide, polysulfone, polyolefin (e.g., polymethylpentene, polyethylene, polypropylene), polystyrene, polyvinyl chloride, polyamide, and polyimide. Examples of metals include aluminum and titanium. Examples of metal oxides include aluminum oxide and titanium oxide. Examples of cellulose include pulp. Preferably, the base material contains at least one selected from the group consisting of PTFE, polyester, polyphenylene sulfide, polysulfone, polyolefin, polyvinyl chloride, polyamide, polyimide, glass, metals, metal oxides, carbon, and cellulose. Among these, PTFE is preferred in terms of its excellent heat resistance and chemical resistance. There are no particular restrictions on the shape of the substrate, and various shapes such as sheets, fibers, tubes, and others are exemplified. The film thickness of a sheet-like substrate is, for example, 30 to 100 μm. The substrate may be porous or non-porous. The material of the porous substrate can be the same as described above. As for the porous substrate, stretched PTFE film or stretched polyolefin film is preferred in terms of excellent breathability and water repellency, and stretched PTFE film is more preferred. Porous materials can be made by stretching PTFE or polyolefin. The pore size of the porous substrate is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and also preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. The lower and upper limits can be combined as appropriate. For example, they may be 0.01 to 5 μm, 0.05 to 5 μm, 0.1 to 5 μm, 0.1 to 3 μm, or 0.1 to 1 μm. If the pore diameter is greater than or equal to the lower limit, it is easier to ensure sufficient air permeability even after surface treatment. If the pore diameter is less than or equal to the upper limit, the effect of improving oil repellency when treated with this treatment agent is excellent. The film thickness of the porous substrate is, for example, 30 to 100 μm.

[0088] Examples of articles include separation membranes, fibers, fabrics, and textile products. Examples of separation membranes include filtration membranes, ventilation filters, ion exchange membranes, and diaphragms. Examples of textile products include clothing such as sportswear, coats, jackets, work clothes, and uniforms, as well as bags and industrial materials. Separation membranes are preferred as articles, and ventilation filters are more preferred. When the article is a separation membrane, the substrate is a porous substrate. Examples of porous substrates are the same as those described above.

[0089] [Method for Manufacturing Articles] Articles of this disclosure can be manufactured, for example, by treating the surface of a substrate with the treatment agent. There are no particular restrictions on the treatment method, and known methods can be applied. For example, if the treatment agent contains a liquid medium, a separation film can be obtained by applying the treatment agent to the substrate and drying it. There are no particular restrictions on the application method, and known wet coating methods or casting methods can be applied. The drying method only needs to remove the liquid medium, and can be either heat drying or non-heat drying. The drying temperature is preferably 20 to 80°C, and more preferably 30 to 80°C.

[0090] When the polymerizable reactive group of the monomer component forming polymer I is a reactive silyl group, the separation membrane can also be produced by coating a substrate with a solution containing the monomer component and then allowing polymerization to proceed using moisture in the air. In this case, a solution in which the monomer component is dissolved in the organic solvent or aqueous medium is applied to the substrate and dried. The application method and drying method may be the same as in the method described above. A steam-containing atmosphere is preferred for drying.

[0091] The present disclosure will be described in more detail below with reference to examples and comparative examples, but the present disclosure is not limited to the following examples unless it exceeds the gist of the disclosure. Examples 1 to 4 are examples, and Example 5 is a comparative example.

[0092] (Evaluation Method) <Mass-average molecular weight (Mw)> For fluorine-containing polymers, Mw was measured using gel permeation chromatography (GPC) (Tosoh Corporation, instrument name "HLC-8420GPC"). Tetrahydrofuran (hereinafter also referred to as "THF") was used as the mobile phase. The Mw of fluorine-containing polymers was converted from the measured values ​​of a standard substance of polystyrene (Agilent Technologies).

[0093] <Solubility in Non-Fluorine Solvents (10% by Mass)> 10 parts by mass of the fluorine-containing polymer and 90 parts by mass of the non-fluorine solvent were mixed and stirred in a mixing rotor for 1 hour. The solution state of the fluorine-containing polymer was then visually inspected, and the solubility of the fluorine-containing polymer was determined according to the following criteria. Methyl ethyl ketone (MEK), butyl acetate, and 1,4-dioxane were used as the non-fluorine solvents. A: Completely soluble. B: Some insoluble matter present. C: Insoluble.

[0094] <Glass transition temperature (Tg), melting point (Tm)> For fluorine-containing polymers, Tg and Tm were measured using a differential scanning calorimetry system (NETZSCH, system name "DSC204F1Phoenix") under the conditions of scanning temperature range -50 to 200°C and scanning speed 10°C / min, repeating heating and cooling for 3 cycles. The Tg and Tm values ​​for the fluorine-containing polymers were taken from the measurements taken in the second cycle.

[0095] <5% Pyrolysis Temperature (5% Td)> For fluorine-containing polymers, the 5% Td was measured using a differential thermogravimetric analyzer (Hitachi High-Tech Corporation, device name "STA7000") under air conditions, scanning temperature 20-550°C, and scanning speed 10°C / min.

[0096] <Heat Resistance Assessment> Heat resistance was assessed according to the following criteria: A: 5%Td is 200°C or higher. B: 5%Td is 150°C or higher but less than 200°C. C: 5%Td is less than 150°C.

[0097] <Water Contact Angle> After dropping an appropriate amount of the prepared surface treatment agent onto a glass substrate, the spin coater was operated at 500 rpm (500 revolutions per minute) for 30 seconds to coat the entire substrate with the surface treatment agent. The substrate was then heated at 110°C for 30 minutes to form a coating of the surface treatment agent. At 25°C, with the coating fixed horizontally, approximately 2 μL of distilled water was dropped onto the coating, and the contact angle was measured using a contact angle meter (Kyowa Interface Science Co., Ltd., device name "SA-301"). The average value measured at five locations on the coating was defined as the water contact angle. The 2θ method was used to calculate the water contact angle. A larger water contact angle indicates superior water repellency and water resistance.

[0098] <Hexadecane Contact Angle> The hexadecane contact angle was measured in the same manner as the water contact angle, except that hexadecane was used instead of water. A larger hexadecane contact angle indicates superior oil repellency and oil resistance.

[0099] <Determination of Coating Contact Angle> The coating contact angle was determined according to the following criteria: A: Hexadecane contact angle is 50° or more. B: Hexadecane contact angle is 40° or more and less than 50°. C: Hexadecane contact angle is less than 40°.

[0100] <Air Permeability> The fabricated separation membrane was used as a sample, and an air permeability evaluation device (Garley Hill S.P.S. Tester, manufactured by Kumagai Riki Kogyo Co., Ltd.) was used. The time required for 100 cc of air to pass through was measured according to JIS P 8117:2009. This value was defined as the air permeability. This value was measured in the in-plane direction of the sample. The air permeability of the porous substrate of the separation membrane (stretched PTFE membrane before coating with surface treatment agent) was measured in the same manner as above, and this value was used as the reference. The reference was 15.4 seconds. The difference between the sample's air permeability and the reference (sample's air permeability - reference's air permeability) was calculated, and the air permeability was determined according to the following criteria: A: Difference from reference is within 2 seconds. B: Difference from reference is greater than 2 seconds but within 5 seconds. C: Difference from reference is greater than 5 seconds.

[0101] (Example 1) <Synthesis of Trifluoromethoxyethyl Methacrylate> In a 50 mL round-bottom flask, 1.4 g (11 mmol) of 2-trifluoromethoxyethanol, 0.015 g (0.0068 mmol) of dibutylhydroxytoluene (hereinafter also referred to as "BHT"), 40 g (470 mmol) of dichloromethane, and 1.5 g (15 mmol) of triethylamine were added and stirred, then cooled to 10°C. 1.5 g (14 mmol) of methacryl chloride was added to this solution, and the mixture was returned to 25°C and stirred for 1 hour. After the reaction was complete, saturated sodium bicarbonate solution was added to the reaction mixture to extract the organic layer, which was then washed with 2 M hydrochloric acid solution and saturated brine. The resulting solution was dried over sodium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 20:1) to obtain 1.1 g of trifluoromethoxyethyl methacrylate (yield 50%). The structure of trifluoromethoxyethyl methacrylate was confirmed by the following NMR. １ H-NMR (CDCl ３ , 400MHz) δ6.19 (s, 1H), 5.66-5.64 (m, 1H), 4.41 (t, 2H), 4.23 (t, 2H), 1.99 (s, 3H).

[0102] <Synthesis of Fluorine-Containing Polymer A> In a 100 mL pressure-resistant glass reactor, 1.0 g of trifluoromethoxyethyl methacrylate, 0.01 g of V-601 (2,2'-azobis(isobutyrate)dimethyl), and 4 g of toluene were charged. A magnetic stirring bar was added, and the liquid phase was bubbling with nitrogen gas for 5 minutes. The internal temperature was raised to 70°C, and the mixture was stirred at a speed of 300 rpm for 24 hours. After purging the nitrogen gas from the gas phase, the reactor was opened to obtain a viscous liquid. The solid components of this viscous liquid were condensed with methanol. The obtained solid components were vacuum-dried at 65°C to obtain 0.85 g of white fluorine-containing polymer A.

[0103] <Preparation of surface treatment agent> A fluorine-containing polymer A was dissolved in MEK to a concentration of 2% by mass to obtain a surface treatment agent.

[0104] <Preparation of Separation Membrane> The prepared surface treatment agent was dropped onto a stretched PTFE film (manufactured by Advantec, pore size 0.2 μm, film thickness 80 μm), coated by bar coating, and heated and dried at 80°C to obtain a separation membrane. The amount of surface treatment agent applied was such that the amount of fluorine-containing polymer A attached per unit area of ​​the stretched PTFE film was 2.5 × 10⁻⁶. －４ g / cm ２ This amount was determined to be the amount that would result in this.

[0105] (Example 2) <Synthesis of Trifluoromethoxystearyl Methacrylate> "Synthesis of Compound a" In a glove box under a nitrogen atmosphere, 6.0 g (18 mmol) of 18-bromo-1-ocdatecene was placed in a 200 mL round-bottom flask and dissolved in 47 g (1,140 mmol) of acetonitrile. 13 g (37 mmol) of nonafluoro-1-butanesulfonic acid trifluoromethyl was added and stirred, cooled to -20°C, and 3.4 g (27 mmol) of silver(I) fluoride was added and stirred. The reaction mixture was returned to 25°C, then heated to 50°C and reacted for 15 hours. After the reaction was complete, water was added to the reaction mixture and extracted with ethyl acetate. The organic layer was washed with saturated brine, then dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (100% hexane) to obtain compound a (CF ３ O-C １６ H ３２ -CH=CH ２ 4.6 g of compound a was obtained (yield 76%). The structure of compound a was confirmed by the following NMR. １ H-NMR (CDCl ３ , 400MHz) δ5.82 (m, 1H), 4.99 (dd, 1H), 4.93 (dd, 1H), 3.94 (t, 2H), 2.03 (m, 2H), 1.68 (m, 2H), 1.42-1.25 (m, 26H).

[0106] "Synthesis of Compound B" 3.6 g (10.7 mmol) of compound a and 60 mL of THF were placed in a 100 mL round-bottom flask and stirred, then cooled to -10°C. 45 mL (23 mmol) of 0.5 M 9-BBN (9-borabicyclo[3,1,1]nonane) THF solution was added to this solution, and the mixture was returned to 25°C and stirred for 24 hours. 12 mL (6 M sodium hydroxide aqueous solution) and 9 mL (30% hydrogen peroxide solution) were added to this solution and the mixture was stirred at 50°C for 6 hours. After the reaction was complete, the mixture was returned to 25°C, and the reaction solution was added to water to precipitate. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 10:1) to obtain compound b (CF ３ O-C １８ H ３６ 3.0 g of compound b (-OH) was obtained (yield 79%). The structure of compound b was confirmed by the following NMR. １ H-NMR (CDCl ３ , 400MHz) δ 3.94 (t, 2H), 3.72 (t, 2H) 1.68 (m, 2H), 1.56 (m, 2H) 1.42-1.25 (m, 28H).

[0107] "Synthesis of Trifluoromethoxystearyl Methacrylate" 1.5 g (4.2 mmol) of compound b, 30 mL of THF, and 0.60 g (6.0 mmol) of triethylamine were placed in a 100 mL round-bottom flask. The mixture was stirred and cooled to 10°C. 0.53 g (51 mmol) of methacryl chloride was added to this solution, and the mixture was stirred for 1 hour at 25°C. After the reaction was complete, the reaction solution was concentrated under reduced pressure, saturated sodium bicarbonate solution was added, and extraction was performed with ethyl acetate. The resulting organic layer was sequentially washed with 2 M hydrochloric acid solution and saturated brine. After drying with sodium sulfate, the layer was concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 20:1) to obtain 1.4 g of trifluoromethoxystearyl methacrylate (yield 76%). The structure of trifluoromethoxystearyl methacrylate was confirmed by the following NMR. １ H-NMR (CDCl ３, 400MHz) δ6.10 (s, 1H), 5.54 (s, 1H), 4.14 (t, 2H), δ 3.94 (t, 2H), 1.99 (s, 3H), 1.75-1.60 (m, 4H), 1.42-1.25 (m, 28H).

[0108] <Synthesis of Fluorine-Containing Polymer B> Except for replacing trifluoromethoxyethyl methacrylate with trifluoromethoxystearyl methacrylate, 0.9 g of white fluorine-containing polymer B was obtained in the same manner as in Example 1.

[0109] <Preparation of surface treatment agent and fabrication of separation membrane> A surface treatment agent was prepared and a separation membrane was fabricated in the same manner as in Example 1, except that fluorine-containing polymer A was replaced with fluorine-containing polymer B.

[0110] (Example 3) <Synthesis of Trifluoromethoxystearyl Acrylate> 1.5 g (42 mmol) of compound b, 30 mL of THF, and 0.60 g (6.0 mmol) of triethylamine were placed in a 100 mL round-bottom flask and stirred, then cooled to 10°C. 0.47 g (51 mmol) of acrylic chloride was added to this solution, and the mixture was returned to 25°C and stirred for 1 hour. After the reaction was complete, the reaction solution was concentrated under reduced pressure, saturated sodium bicarbonate solution was added, and extraction was performed with ethyl acetate. The obtained organic layer was sequentially washed with 2 M hydrochloric acid aqueous solution and saturated brine. After drying with sodium sulfate, it was concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 20:1) to obtain 1.3 g of trifluoromethoxystearyl acrylate (yield 74%). The structure of trifluoromethoxystearyl acrylate was confirmed by the following NMR. １ H-NMR (CDCl ３ , 400MHz) δ6.39 (dd, 1H), 6.12 (dd, 1H), 5.81 (dd, 1H), 4.14 (t, 2H), δ 3.94 (t, 2H), 1.75-1.60 (m, 4H), 1.42-1.25 (m, 28H).

[0111] <Synthesis of Fluorine-Containing Polymer C> Except for replacing trifluoromethoxyethyl methacrylate with trifluoromethoxystearyl acrylate, 0.82 g of white fluorine-containing polymer C was obtained in the same manner as in Example 1.

[0112] <Preparation of surface treatment agent and fabrication of separation membrane> A surface treatment agent was prepared and a separation membrane was fabricated in the same manner as in Example 1, except that fluorine-containing polymer A was replaced with fluorine-containing polymer C.

[0113] (Example 4) <Synthesis of [3-trifluoromethoxy-2,2'-bis(trifluoromethoxymethyl)propyl]methacrylate> Following the reaction pathway shown below, [3-trifluoromethoxy-2,2'-bis(trifluoromethoxymethyl)propyl]methacrylate ((CF ３ O-CH ２ -) ３ C-CH ２ -OC(=O)C(CH ３ ) = CH ２ ) was synthesized.

[0114]

[0115] "Synthesis of compounds c, d, and e" Compounds c, d, and e were synthesized using the method described in Tetrahedron 2007, 63, 3982-3988.

[0116] "Synthesis of Compound f" In a glove box under a nitrogen atmosphere, 1.0 g (4.4 mmol) of compound e, 17 g (66 mmol) of silver trifluoromethanesulfonate, 9.4 g (27 mmol) of SelectFluor®, 12 g (80 mmol) of cesium fluoride, 8.4 g (27 mmol) of N-fluorobenzenesulfonimide, and 90 g (972 mmol) of toluene were added to a 300 mL round-bottom flask and stirred. To this mixture, 6.4 g (66 mmol) of 2-fluoropyridine and 9.4 g (66 mmol) of trifluoromethyltrimethylsilane were added and stirred for 16 hours. After the reaction was complete, the reaction solution was passed through 30 g of silica gel and eluted with ethyl acetate. The obtained solution was concentrated under reduced pressure and purified by silica gel column chromatography (hexane:ethyl acetate = 9:1) to obtain compound f (1.4 g, 74% yield). The structure of compound f was confirmed by the following NMR. １ H-NMR (CDCl ３, 400MHz) δ7.35-7.16 (m, 5H), 4.52 (s, 2H), 4.05 (s, 6H), 3.50 (s, 2H).

[0117] "Synthesis of compound g" 1.4 g (3.3 mmol) of compound f and 20 mL of methanol were added to a 100 mL round-bottom flask, and 1.4 g of Pd / C (palladium-carbon with 5% by mass palladium content) (hydrated) was added under a nitrogen atmosphere. The flask was then purged three times with hydrogen and stirred at 25°C for 16 hours. Pd / C was then removed by Celite filtration, and the filtrate was removed under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 10:1) to obtain 1.0 g of compound g (yield 90%). The structure of compound g was confirmed by the following NMR. １ H-NMR (CDCl ３ , 400MHz) δ4.05 (s, 6H), 3.75 (d, 2H), 1.62 (t, 1H).

[0118] "Synthesis of [3-trifluoromethoxy-2,2'-bis(trifluoromethoxymethyl)propyl]methacrylate" In a 100 mL round-bottom flask, 1.0 g (2.9 mmol) of compound g, 20 mL of THF, and 0.41 g (4.1 mmol) of triethylamine were added and stirred, and the mixture was cooled to 10°C. 0.37 g (3.6 mmol) of methacrylic chloride was added to this solution, and the mixture was stirred for 1 hour at 25°C. After the reaction was complete, the reaction solution was concentrated under reduced pressure, saturated sodium bicarbonate solution was added, and extraction was performed with ethyl acetate. The resulting organic layer was sequentially washed with 2 M hydrochloric acid aqueous solution and saturated brine. After drying with sodium sulfate, the mixture was concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 20:1) to obtain 1.0 g of [3-trifluoromethoxy-2,2'-bis(trifluoromethoxymethyl)propyl]methacrylate (yield 83%). The structure of [3-trifluoromethoxy-2,2'-bis(trifluoromethoxymethyl)propyl]methacrylate was confirmed by the following NMR. １ H-NMR (CDCl ３, 400MHz) δ6.10 (s, 1H), 5.54 (s, 1H), δ4.05 (s, 6H), 3.75 (d, 2H), 1.99 (s, 3H).

[0119] <Synthesis of Fluorine-Containing Polymer D> 0.9 g of white fluorine-containing polymer D was obtained in the same manner as in Example 1, except that trifluoromethoxyethyl methacrylate was replaced with [3-trifluoromethoxy-2,2'-bis(trifluoromethoxymethyl)propyl]methacrylate.

[0120] <Preparation of surface treatment agent and fabrication of separation membrane> A surface treatment agent was prepared and a separation membrane was fabricated in the same manner as in Example 1, except that fluorine-containing polymer A was replaced with fluorine-containing polymer D.

[0121] (Example 5) As a fluorine-containing polymer, Teflon® AF 1600X (tetrafluoroethylene (TFE)-perfluoro-(2,2-dimethyl-1,3-dioxole) (PDD) copolymer) from Mitsui Chemours Fluoroproducts was prepared. Teflon® AF 1600X was dissolved in 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane to a concentration of 2% by mass to obtain a surface treatment agent. The obtained surface treatment agent was coated onto a PTFE film in the same manner as in Example 1, and heated and dried to obtain a separation film.

[0122] Table 1 shows the monomer composition, Mw, solubility and heat resistance in non-fluorine solvents, contact angle of the surface treatment coating, and evaluation results of the separation membrane for each example of fluorine-containing polymer. Note that a "-" for Tm indicates the absence of Tm, and a "-" for Tg indicates the absence of Tg.

[0123]

[0124] The separation membranes using the surface treatment agents in Examples 1-4 exhibited superior breathability compared to Example 5. Furthermore, the fluorine-containing polymers in the surface treatment agents in Examples 1-4 showed excellent solubility in non-fluorine solvents and possessed sufficient heat resistance. The reason for the superior breathability is likely that the fluorine-containing polymers become dense on the surface of the porous substrate, forming a uniform coating without filling the pores.

[0125] The surface treatment agent disclosed herein contains a polymer soluble in a non-fluorine solvent and can be used on articles with excellent breathability. Examples of articles include separation membranes, fibers, fabrics, and textile products. Examples of separation membranes include filtration membranes, breathable filters, ion exchange membranes, and diaphragms. Examples of textile products include clothing such as sportswear, coats, jackets, work clothes, and uniforms, as well as bags and industrial materials.

Claims

1. A surface treatment agent comprising a polymer having units based on the compound represented by formula 1 below. T-A-(OR ｆ ) ｍ ... (1) However, T is a monovalent polymerizable group, A is a (1+m)valent linking group that does not have a fluorine atom or an aromatic ring, and R ｆ m is a perfluoroalkyl group having 1 to 6 carbon atoms, and m is an integer greater than or equal to 1.

2. The surface treatment agent according to claim 1, which is for use with separation membranes.

3. R ​​in formula 1 above ｆ The surface treatment agent according to claim 1 or 2, wherein the group is a trifluoromethyl group.

4. The surface treatment agent according to claim 1 or 2, wherein A in formula 1 is a (1+m) valent saturated hydrocarbon group.

5. The surface treatment agent according to claim 1 or 2, wherein T in formula 1 is a group having a polymerizable unsaturated bond, a group containing a cyclic ether structure, or a reactive silyl group.

6. The surface treatment agent according to claim 1 or 2, wherein T in formula 1 is a (meth)acryloyloxy group or a (meth)acrylamide group.

7. The surface treatment agent according to claim 1 or 2, wherein the content of units based on the compound in the polymer is 5% by mass or more relative to the total number of units constituting the polymer.

8. The surface treatment agent according to claim 1 or 2, wherein the mass-average molecular weight of the polymer is 5,000 to 800,000.

9. The surface treatment agent according to claim 1 or 2, further comprising a liquid medium.

10. The surface treatment agent according to claim 9, wherein the liquid medium comprises a solvent that does not contain fluorine atoms.

11. The surface treatment agent according to claim 1 or 2, wherein the content of the polymer is 0.5 to 30% by mass with respect to the total mass of the surface treatment agent.

12. A method for producing a surface treatment agent, comprising polymerizing a monomer component containing a compound represented by the following formula 1 in the presence of a polymerization initiator. T-A-(OR ｆ ) ｍ ... (1) However, T is a monovalent polymerizable group, A is a (1+m)valent linking group that does not have a fluorine atom or an aromatic ring, and R ｆ m is a perfluoroalkyl group having 1 to 6 carbon atoms, and m is an integer greater than or equal to 1.

13. An article comprising a substrate and a polymer having a unit based on a compound represented by the following formula (1) adhered to the surface of the substrate. T-A-(OR ｆ ) ｍ ... (1) However, T is a monovalent polymerizable group, A is a (1 + m)-valent linking group having no fluorine atom and no aromatic ring, R ｆ is a perfluoroalkyl group having 1 to 6 carbon atoms, and m is an integer of 1 or more.

14. The article according to claim 13, wherein the separation membrane is a porous substrate.

15. The amount of polymer adhering to the substrate is 1 × 10⁻¹⁶ per unit area. －６ ~5 x 10 －３ g / cm ２ The article according to claim 13 or 14.

16. The article according to claim 13 or 14, wherein the substrate comprises at least one selected from the group consisting of polytetrafluoroethylene, polyester, polyphenylene sulfide, polyolefin, polystyrene, polyvinyl chloride, polyamide, polyimide, glass, metal, metal oxide, carbon, and cellulose.

17. A method for manufacturing an article, comprising treating the surface of a substrate with a surface treatment agent according to claim 1 or 2.

18. The method for manufacturing an article according to claim 17, wherein the article is a separation membrane and the substrate is a porous substrate.

19. The method for producing an article according to claim 17, wherein the substrate comprises at least one selected from the group consisting of polytetrafluoroethylene, polyester, polyphenylene sulfide, polyolefin, polystyrene, polyvinyl chloride, polyamide, polyimide, glass, metal, metal oxide, carbon, and cellulose.

20. The method for producing an article according to claim 18, wherein the substrate comprises at least one selected from the group consisting of polytetrafluoroethylene, polyester, polyphenylene sulfide, polyolefin, polystyrene, polyvinyl chloride, polyamide, polyimide, glass, metal, metal oxide, carbon, and cellulose.

21. Compounds represented by formula 1A below. ２ -A-(OCF) ３ ) ｍ ... (1A) However, T ２ A is a (meth)acryloyloxy group or a (meth)acrylamide group, A is a (1+m) valent linking group that does not have a fluorine atom or an aromatic ring, and m is an integer of 1 or more.

22. A polymer having units based on the compound represented by formula 1A below. ２ -A-(OCF) ３ ) ｍ ... (1A) However, T ２ A is a (meth)acryloyloxy group or a (meth)acrylamide group, A is a (1+m) valent linking group that does not have a fluorine atom or an aromatic ring, and m is an integer of 1 or more.

23. The polymer according to claim 22, wherein the content of units based on the compound is 5% by mass or more relative to the total number of units constituting the polymer.

24. The polymer according to claim 22 or 23, wherein the mass-average molecular weight is 5,000 to 800,000.

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