Water and oil repellent composition, method for producing the same, and article

Abstract

Provided is a water- and oil-repelling agent composition with which an article that has a high resistance to water pressure and a low water absorption rate can be obtained. This water- and oil-repelling agent composition includes a fluorine-including polymer having a unit that is based on a monomer (a), a unit that is based on a monomer (b1), a unit that is based on a monomer (b2), a unit that is based on a monomer (b3), and a unit that is based on a monomer (c), wherein in relation to all of the units that make up the fluorine-including polymer, the proportion of the unit that is based on the monomer (a) is 70-80 mass%, the total proportion of the unit that is based on the monomer (b1), the unit that is based on the monomer (b2), and the unit that is based on the monomer (b3) is 12-28 mass%, and the proportion of the unit that is based on the monomer (c) is 2-8 mass%. Monomer (a): A compound represented by (Z–Q)nX. Monomer (b1): A monomer that has a C22 alkyl group and does not have a polyfluoroalkyl group (Rf group). Monomer (b2): A monomer that has a C20 alkyl group and does not have an Rf group. Monomer (b3): A monomer that has a C18 alkyl group and does not have an Rf group. Monomer (c): A halogenated olefin.

Description

Technical Field

[0001] The present invention relates to a water- and oil-repellent composition, a method for producing the same, and an article.

Background Art

[0002] As a method for imparting water- and oil-repellency to the surface of an article, a method of treating an article using a water- and oil-repellent composition in which a copolymer having a unit based on a monomer having a polyfluoroalkyl group is dispersed in a liquid medium is known.

[0003] Patent Document 1 proposes a water- and oil-repellent composition containing a copolymer having a unit based on a monomer having a polyfluoroalkyl group and a unit based on a monomer having a hydrocarbon group having 14 or more carbon atoms, and a copolymer having a unit based on a monomer having a polyfluoroalkyl group and a unit based on a monomer having a functional group capable of crosslinking.

[0004] Patent Document 2 proposes a water- and oil-repellent composition for an air filter containing a copolymer having a unit based on a monomer having a polyfluoroalkyl group, a unit based on a monomer having an alkyl group having 20 to 30 carbon atoms, and a unit based on a halogenated olefin.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, according to the study by the present inventor, the air filter treated with the water- and oil-repellent composition of Patent Documents 1 and 2 may have a low water pressure resistance and a high water absorption rate.

[0007] The present invention provides a water and oil repellent composition capable of obtaining an article with high water pressure resistance and low water absorption rate, a method for producing the same, and an article with high water pressure resistance and low water absorption rate.

Means for Solving the Problems

[0008] The present invention has the following aspects. [1] A water and oil repellent composition containing a fluorine-containing polymer having units based on the following monomer (a), units based on the following monomer (b1), units based on the following monomer (b2), units based on the following monomer (b3), and units based on the following monomer (c), wherein, based on all the units constituting the fluorine-containing polymer, the proportion of the units based on the monomer (a) is 70 to 80% by mass, the total proportion of the units based on the monomer (b1), the units based on the monomer (b2), and the units based on the monomer (b3) is 12 to 28% by mass, and the proportion of the units based on the monomer (c) is 2 to 8% by mass. Monomer (a): (Z-Q) n A compound represented by X. However, Z is a polyfluoroalkyl group having 1 to 6 carbon atoms or C j F 2j+1 O(CFX 1 CF2O) k CFX 2 -represents a group, j is an integer from 1 to 6, k is an integer from 0 to 10, X 1 and X 2 are each independently a fluorine atom or a trifluoromethyl group, Q is a divalent organic group or a single bond, n is 1 or 2, X is, when n is 1, a group represented by -CR=CH2, -C(O)OCR=CH2, -OC(O)CR=CH2, -OCH2-φ-CR=CH2 or -OCH=CH2; when n is 2, -CH[-(CH2) m CR=CH2]-, -CH[-(CH2) m C(O)OCR=CH2]-, -CH[-(CH2) ma group represented by -OC(O)CR=CH2- or -OC(O)CH=CHC(O)O-, R is a hydrogen atom, a methyl group or a halogen atom, φ is a phenylene group, and m is an integer of 0 to 4. Monomer (b1): A monomer having no polyfluoroalkyl group and having an alkyl group with 22 carbon atoms. Monomer (b2): A monomer having no polyfluoroalkyl group and having an alkyl group with 20 carbon atoms. Monomer (b3): A monomer having no polyfluoroalkyl group and having an alkyl group with 18 carbon atoms. Monomer (c): A halogenated olefin. [2] With respect to the total of the unit based on the monomer (b1), the unit based on the monomer (b2), and the unit based on the monomer (b3), the proportion of the unit based on the monomer (b1) is 60 to 80% by mass, the proportion of the unit based on the monomer (b2) is 10 to 20% by mass, and the proportion of the unit based on the monomer (b3) is 10 to 20% by mass, the water and oil repellent composition according to [1]. [3] The water and oil repellent composition according to [1] or [2], wherein each of the monomer (b1), the monomer (b2), and the monomer (b3) is acrylate or methacrylate. [4] The water and oil repellent composition according to any one of [1] to [3], wherein Z of the monomer (a) is a polyfluoroalkyl group having 1 to 6 carbon atoms, n is 1, and X is a group represented by -CR=CH2 or -OC(O)CR=CH2. [5] The water and oil repellent composition according to [4], wherein Z of the monomer (a) is a polyfluoroalkyl group having 6 carbon atoms. [6] The water and oil repellent composition according to any one of [1] to [5], which does not contain a cationic surfactant. [7] The water and oil repellent composition according to any one of [1] to [6], which does not contain an organic solvent having a boiling point of 280 °C or lower at atmospheric pressure. [8] A method for obtaining a water and oil repellent composition containing a fluorine-containing polymer by polymerizing a monomer component in the presence of a polymerization initiator, wherein the monomer component includes the following monomer (a), the following monomer (b1), the following monomer (b2), the following monomer (b3), and the following monomer (c), A method for producing a water and oil repellent composition, wherein the proportion of the monomer (a) is 70 to 80% by mass, the total proportion of the monomers (b1), (b2) and (b3) is 12 to 28% by mass, and the proportion of the monomer (c) is 2 to 8% by mass, based on the total amount of the monomer components. Monomer (a): (Z-Q) n A compound represented by X. However, Z is a polyfluoroalkyl group having 1 to 6 carbon atoms or C j F 2j+1 O(CFX 1 CF2O) k CFX 2 -represents a group, j is an integer of 1 to 6, k is an integer of 0 to 10, X 1 and X 2 are each independently a fluorine atom or a trifluoromethyl group, Q is a divalent organic group or a single bond, n is 1 or 2, X is, when n is 1, a group represented by -CR=CH2, -C(O)OCR=CH2, -OC(O)CR=CH2, -OCH2-φ-CR=CH2 or -OCH=CH2; when n is 2, a group represented by -CH[-(CH2) m CR=CH2]-, -CH[-(CH2) m C(O)OCR=CH2]-, -CH[-(CH2) m OC(O)CR=CH2]- or -OC(O)CH=CHC(O)O-, R is a hydrogen atom, a methyl group or a halogen atom, φ is a phenylene group, and m is an integer of 0 to 4. Monomer (b1): A monomer having no polyfluoroalkyl group and having an alkyl group with 22 carbon atoms. Monomer (b2): A monomer having no polyfluoroalkyl group and having an alkyl group with 20 carbon atoms. Monomer (b3): A monomer having no polyfluoroalkyl group and having an alkyl group with 18 carbon atoms. Monomer (c): A halogenated olefin. [9] The production method of the water and oil repellent composition according to [8], wherein the proportion of the monomer (b1) is 60 to 80% by mass, the proportion of the monomer (b2) is 10 to 20% by mass, and the proportion of the monomer (b3) is 10 to 20% by mass, based on the total of the monomer (b1), the monomer (b2), and the monomer (b3).

[10] The production method of the water and oil repellent composition according to [8] or [9], wherein all of the monomer (b1), the monomer (b2), and the monomer (b3) are acrylate or methacrylate.

[11] The production method of the water and oil repellent composition according to [9] or

[10] , wherein the monomer component is polymerized in a medium containing water in the presence of the polymerization initiator and the surfactant.

[12] The production method of the water and oil repellent composition according to

[11] , wherein the surfactant does not contain a cationic surfactant.

[13] The production method of the water and oil repellent composition according to

[11] or

[12] , wherein the medium does not contain an organic solvent having a boiling point of 280 °C or lower at atmospheric pressure.

[14] An article treated with the water and oil repellent composition according to any one of [1] to [7].

[15] The article according to

[14] , which is an air filter.

Advantages of the Invention

[0009] According to the water and oil repellent composition of the present invention, an article having high water pressure resistance and low water absorption rate can be obtained. According to the production method of the water and oil repellent composition of the present invention, a water and oil repellent composition capable of obtaining an article having high water pressure resistance and low water absorption rate can be produced. The article of the present invention has high water pressure resistance and low water absorption rate.

Embodiments for Carrying Out the Invention

[0010] The meanings and definitions of the terms in the present invention are as follows. "Unit based on monomer" is a general term for an atomic group directly formed by the polymerization of one molecule of monomer and an atomic group obtained by chemically converting a part of the atomic group. "(Meth)acrylate" is a generic term for acrylate and methacrylate. Similarly, "(meth)acryloyl" is a generic term for acryloyl and methacryloyl, and "(meth)acrylamide" is a generic term for acrylamide and methacrylamide. The number average molecular weight (hereinafter also referred to as "Mn") and the weight average molecular weight (hereinafter also referred to as "Mw") of the polymer are the molecular weights in terms of polymethyl methacrylate measured by gel permeation chromatography (hereinafter also referred to as "GPC"). The solid content concentration is calculated by (solid content mass / sample mass) × 100, where the mass of the sample before heating is taken as the sample mass and the mass after drying the sample in a convection dryer at 120°C for 4 hours is taken as the solid content mass. "~" indicating a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value.

[0011] [Water and oil repellent composition] The water and oil repellent composition of the present invention (hereinafter also referred to as "this composition") contains a specific fluorine-containing polymer (hereinafter also referred to as "polymer A"). This composition typically contains a medium. This composition may optionally contain a surfactant. This composition may optionally contain other components.

[0012] (Polymer A) Polymer A has units based on monomer (a) (hereinafter also referred to as "unit (a)"), units based on monomer (b1) (hereinafter also referred to as "unit (b1)"), units based on monomer (b2) (hereinafter also referred to as "unit (b2)"), units based on monomer (b3) (hereinafter also referred to as "unit (b3)"), and units based on monomer (c) (hereinafter also referred to as "unit (c)"). Polymer A may optionally have units based on other monomers.

[0013] [Monomer (a)] Monomer (a) is (Z-Q) nIt is a compound represented by X.

[0014] Z is a polyfluoroalkyl group having 1 to 6 carbon atoms (hereinafter, the polyfluoroalkyl group is also referred to as "R f group").) or C j F 2j+1 O(CFX 1 CF2O) k CFX 2 -represents a group, j is an integer from 1 to 6, k is an integer from 0 to 10, and X 1 and X 2 are each independently a fluorine atom or a trifluoromethyl group. R f As the group, a perfluoroalkyl group (hereinafter, also referred to as "R F group") is preferred. The R f group may be linear or branched, and linear is preferred. Examples of Z include F(CF2)4-, F(CF2)5-, F(CF2)6-, (CF3)2CF(CF2)2-, C j F 2j+1 O[CF(CF3)CF2O] k CF(CF3)- and the like.

[0015] Q is a divalent organic group or a single bond. In the monomer (a), the boundary between Z and Q is defined so that the carbon number of Z is minimized. As the divalent organic group, an alkylene group or an alkenylene group is preferred, and an alkylene group is more preferred. The alkylene group may be linear or branched. The alkylene group may have -O-, -NH-, -CO-, -S-, -SO2-, or -CX 3 =CX 4 -(provided that X 3 and X 4 are each independently a hydrogen atom or a methyl group.) at the carbon atom-carbon atom or at the terminal on the side bonded to Z.

[0016] Examples of Q include -CH2-, -CH2CH2-, -(CH2)3-, -CH2CH2CH(CH3)-, -CH=CH-CH2-, -S-CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-SO2-CH2CH2-, -X 5 -OC(O)NH-A-NHC(O)O-(C p H2 p )-. However, p is an integer from 2 to 30, A is an unbranched symmetric alkylene group, arylene group or aralkylen group, and X 5 is -SO2NX 6 -C d H 2d -, -CONHC d H 2d -, -CH(R F1 )-C e H 2e - or -C q H 2q -. X 6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, d is an integer from 2 to 8, R F1 is an R F group having 1 to 20 carbon atoms, e is an integer from 0 to 6, and q is an integer from 1 to 20. R F1 is preferably an R F group having 1 to 6 carbon atoms, and more preferably an R F group having 4 to 6 carbon atoms.

[0017] n is 1 or 2. When n is 1, X is a group represented by -CR=CH2, -C(O)OCR=CH2, -OC(O)CR=CH2, -OCH2-φ-CR=CH2 or -OCH=CH2. When n is 2, X is a group represented by -CH[-(CH2) m CR=CH2]-, -CH[-(CH2) m C(O)OCR=CH2]-, -CH[-(CH2) m OC(O)CR=CH2]- or -OC(O)CH=CHC(O)O-. However, R is a hydrogen atom, a methyl group or a halogen atom, φ is a phenylene group, and m is an integer from 0 to 4.

[0018] As the monomer (a), a monomer having 1 to 6 carbon atoms is preferably used in terms of polymerizability with other monomers, flexibility of a film containing the polymer A, adhesion of the polymer A to an article, dispersibility in a medium, or ease of emulsion polymerization. F An olefin or (meth)acrylate having a R F More preferably, Z is an olefin or (meth)acrylate having a group. F group, Q is an alkylene group having 1 to 4 carbon atoms, n is 1, and X is -CR=CH2 or -C(O)OCR=CH2, and Z is R F More preferred is a compound in which Q is a group, Q is an alkylene group having 1 to 4 carbon atoms, n is 1, and X is -CR=CH2 or -C(O)OCR=CH2. Two or more kinds of monomers (a) may be used in combination.

[0019] <Monomer (b1)> The monomer (b1) is R f It is a monomer having no group and having an alkyl group with 22 carbon atoms. Examples of the monomer (b1) include (meth)acrylates having an alkyl group with 22 carbon atoms, (meth)acrylamides having an alkyl group with 22 carbon atoms, vinyl ethers having an alkyl group with 22 carbon atoms, and vinyl esters having an alkyl group with 22 carbon atoms. Among these, (meth)acrylates having an alkyl group with 22 carbon atoms are preferred, and behenyl (meth)acrylate is particularly preferred.

[0020] <Monomer (b2)> The monomer (b2) is R f It is a monomer having no alkyl group and having an alkyl group having 20 carbon atoms. Examples of the monomer (b2) include (meth)acrylate having an alkyl group with 20 carbon atoms, (meth)acrylamide having an alkyl group with 20 carbon atoms, vinyl ether having an alkyl group with 20 carbon atoms, and vinyl ester having an alkyl group with 20 carbon atoms. Among these, (meth)acrylate having an alkyl group with 20 carbon atoms is preferable, and arachidyl (meth)acrylate is particularly preferable.

[0021] <Monomer (b3)> The monomer (b3) is a monomer having no f R group and having an alkyl group with 18 carbon atoms. Examples of the monomer (b3) include (meth)acrylate having an alkyl group with 18 carbon atoms, (meth)acrylamide having an alkyl group with 18 carbon atoms, vinyl ether having an alkyl group with 18 carbon atoms, and vinyl ester having an alkyl group with 18 carbon atoms. Among these, (meth)acrylate having an alkyl group with 18 carbon atoms is preferable, and stearyl (meth)acrylate is particularly preferable. Two or more kinds of the monomer (b1), the monomer (b2), and the monomer (b3) may be used in combination. Since the article processed with the water and oil repellent composition tends to have high water pressure resistance and low water absorption, it is preferable that any of the monomer (b1), the monomer (b2), and the monomer (b3) is acrylate or methacrylate.

[0022] <Monomer (c)> The monomer (c) is a halogenated olefin. As the monomer (c), chlorinated olefin or fluorinated olefin is preferable, and specifically, vinyl chloride, vinylidene chloride, tetrafluoroethylene, and vinylidene fluoride can be mentioned. Among these, vinyl chloride and vinylidene chloride are preferable from the viewpoint of adhesion to the substrate. Two or more kinds of the monomer (c) may be used in combination.

[0023] <Other monomers> The other monomer is a monomer other than monomer (a), monomer (b1), monomer (b2), monomer (b3) and monomer (c). The other monomer only needs to be copolymerizable with monomer (a), monomer (b1), monomer (b2), monomer (b3) and monomer (c). For example, (meth)acrylates, (meth)acrylamides, vinyl ethers and vinyl esters excluding monomer (a), monomer (b1), monomer (b2), monomer (b3) and monomer (c) can be mentioned. Examples of the other monomer include methyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, methylolacrylamide, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and the 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate.

[0024] The proportion of unit (a) relative to all the units constituting polymer A is 70 to 80% by mass, preferably 72 to 78% by mass. If the proportion of unit (a) is within the above range, the article treated with this composition can have high water pressure resistance and low water absorption.

[0025] The total proportion of unit (b1), unit (b2) and unit (b3) relative to all the units constituting polymer A is 12 to 28% by mass, preferably 14 to 26% by mass, and may be 14 to 25% by mass. If the total proportion of unit (b1), unit (b2) and unit (b3) is within the above range, the article treated with this composition can have high water pressure resistance and low water absorption.

[0026] The proportion of unit (b1) relative to the total of unit (b1), unit (b2) and unit (b3) is preferably 60 to 80% by mass, more preferably 64 to 76% by mass. The proportion of unit (b2) relative to the total of unit (b1), unit (b2) and unit (b3) is preferably 10 to 20% by mass, more preferably 12 to 18% by mass. The proportion of unit (b3) relative to the total of unit (b1), unit (b2) and unit (b3) is preferably 10 to 20% by mass, more preferably 12 to 18% by mass. If the ratios of unit (b1), unit (b2), and unit (b3) are within the above ranges, the articles treated with this composition can have higher water pressure resistance and lower water absorption rate. With respect to the total of unit (b1), unit (b2) and unit (b3), the ratio of unit (b1) is preferably 60 to 80% by mass, the ratio of unit (b2) is preferably 10 to 20% by mass, and the ratio of unit (b3) is preferably 10 to 20% by mass. More preferably, the ratio of unit (b1) is 64 to 76% by mass, the ratio of unit (b2) is 12 to 18% by mass, and the ratio of unit (b3) is 12 to 18% by mass. If the ratios of unit (b1), unit (b2), and unit (b3) are within the above ranges, the articles treated with this composition can have higher water pressure resistance and lower water absorption rate.

[0027] The ratio of unit (c) to all the units constituting polymer A is 2 to 8% by mass, preferably 2 to 7% by mass, and may be 3 to 7% by mass. If the ratio of unit (c) is at least the above lower limit value, the adhesion to the base material of polymer A is excellent, and if it is at most the above upper limit value, the articles treated with this composition can have high water pressure resistance and low water absorption rate.

[0028] The ratio of each unit 1 can be calculated by 1H-NMR and the reaction rate of each monomer component by gas chromatography. The ratio of each unit may be calculated based on the charged amount of the monomer components during the production of polymer A.

[0029] The Mn of polymer A is preferably 5000 to 100000, more preferably 10000 to 80000, and even more preferably 15000 to 50000. If the Mn of polymer A is at least the above lower limit value, the articles treated with this composition can have higher water pressure resistance and lower water absorption rate, and if it is at most the above upper limit value, the film-forming property is more excellent. The Mw of polymer A is preferably 10000 to 300000, more preferably 20000 to 200000, and even more preferably 30000 to 150000. If the Mw of polymer A is at least the above lower limit value, the articles treated with this composition can have higher water pressure resistance and lower water absorption rate, and if it is at most the above upper limit value, the film-forming property is more excellent. The polymer A preferably satisfies at least one of the ranges of the Mn and the Mw, and more preferably satisfies both of them.

[0030] (medium) Examples of the medium include an aqueous medium and a medium other than the aqueous medium, and the aqueous medium is preferred.

[0031] The aqueous medium is a medium containing water. Examples of the aqueous medium include water and water containing a water-soluble organic solvent. The water-soluble organic solvent is an organic solvent miscible with water in any ratio. As the water-soluble organic solvent, at least one selected from the group consisting of alcohols (excluding ether alcohols), ether alcohols, and aprotic polar solvents is preferred. Examples of the alcohol include t-butanol and propylene glycol. Examples of the ether alcohol include 3-methoxymethylbutanol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol. Examples of the aprotic polar solvent include N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (hereinafter also referred to as "THF"), acetonitrile, acetone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-3-methyl-1-butanol, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. When the aqueous medium is water containing a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass, more preferably 5 to 60 parts by mass, per 100 parts by mass of water.

[0032] Examples of the medium other than the aqueous medium include water-insoluble media. Examples of the water-insoluble medium include glycols, glycol ethers (excluding ether alcohols), hydrocarbons, ketones, esters, ethers (excluding ether alcohols and glycol ethers), and halogen compounds. These media may contain two or more thereof. Examples of the glycol or glycol ether include diethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. Examples of the hydrocarbon include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. Examples of the aliphatic hydrocarbon include pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, decane, undecane, dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, tetradecane, and hexadecane. Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane. Examples of the aromatic hydrocarbon include benzene, toluene, and xylene. Examples of the ketone include methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, and methyl isobutyl ketone. Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, and methyl propionate. Examples of the ether include diisopropyl ether. Examples of the halogen compound include halogenated hydrocarbons and halogenated ethers. Examples of the halogenated hydrocarbon include hydrochlorofluorocarbons, hydrofluorocarbons, and hydrobromocarbons. Examples of the halogenated ether include hydrofluoroethers. Examples of the hydrofluoroether include separated hydrofluoroethers and non-separated hydrofluoroethers. The separated hydrofluoroether is a compound in which a perfluoroalkyl group or a perfluoroalkylene group, and an alkyl group or an alkylene group are bonded via an etheric oxygen atom. The non-separated hydrofluoroether is a hydrofluoroether containing a partially fluorinated alkyl group or alkylene group.

[0033] From the viewpoint of suppressing outgassing from articles such as air filters, it is preferable that the medium does not contain an organic solvent having a boiling point of 280 ° C or lower at atmospheric pressure. Specifically, it is preferable that the medium does not contain glycol-based hydrophilic media such as dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol, and tetraethylene glycol dimethyl ether. It is particularly preferable that the medium is water.

[0034] (Surfactant) As the surfactant, a surfactant having no fluorine atom is preferable. Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. As the surfactant, from the viewpoint of excellent dispersion stability of the aqueous dispersion containing Polymer A, single use of a nonionic surfactant, combined use of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant, or single use of an anionic surfactant is preferable.

[0035] Examples of the nonionic surfactant include surfactants s described in paragraphs

[0067] to

[0095] of Japanese Patent Application Laid-Open No. 2009-215370 1 ~s 6 are included, and surfactant s 1 ~s3 is preferred. Surfactant s 1 is preferably a polyoxyethylene alkyl ether. Surfactant s 2 is preferably an acetylene glycol ethylene oxide adduct. Surfactant s 3 is preferably a polyoxyethylene polyoxypropylene glycol. Two or more nonionic surfactants may be used in combination. For example, surfactant s 1 and surfactant s 2 may be used in combination.

[0036] Examples of the cationic surfactant include the surfactant s described in paragraphs

[0096] to

[0100] of Japanese Patent Application Laid-Open No. 2009-215370. 7 are exemplified. Surfactant s 7 is preferably an ammonium salt in which one or more hydrogen atoms bonded to a nitrogen atom are substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene chain having a hydroxyl group at the terminal, and a compound s represented by the following formula s 71 is more preferred. 71 is more preferred. [(R 21 )4N + ·X - Formula s 71 R 21 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a polyoxyalkylene chain having a hydroxyl group at the terminal. Four R 21 may be the same or different, but four R 21 are not simultaneously hydrogen atoms. X - is a counter ion. X - is preferably a chloride ion, an ethyl sulfate ion, or an acetate ion. Compound s 71Examples include, for example, monostearyltrimethylammonium chloride, monostearyldimethylethylammonium ethyl sulfate, mono(stearyl)monomethyldi(polyethylene glycol)ammonium chloride, monofluorohexyltrimethylammonium chloride, di(tallow alkyl)dimethylammonium chloride, dimethylmonococonutamine acetate. Two or more cationic surfactants may be used in combination.

[0037] Examples of amphoteric surfactants include the surfactants s described in paragraphs

[0101] to

[0102] of JP-A-2009-215370. 8 can be mentioned. Two or more amphoteric surfactants may be used in combination.

[0038] The content ratio of the cationic surfactant with respect to 100% by mass of the present composition is preferably 0.5% by mass or less, and particularly preferably 0% by mass, because aggregation and sedimentation are less likely to occur when an anionic co-agent is used in combination. That is, it is particularly preferable that the present composition does not contain a cationic surfactant. The water and oil repellent composition, particularly the water and oil repellent composition for air filters, may be used in combination with a co-agent containing an anionic acrylic resin. In this case, the water and oil repellent composition is required to have high compatibility with the anionic acrylic resin (not to aggregate or sediment the anionic acrylic resin). There is a concern that the cationic surfactant may cause an ionic interaction with the anionic acrylic resin and aggregate or sediment the anionic acrylic resin. Nonionic surfactants and anionic surfactants do not cause an ionic interaction with anionic acrylic resins. Therefore, as the surfactant, a nonionic surfactant or an anionic surfactant is preferable.

[0039] (Other components) Examples of other components include fluorine-containing polymers other than polymer A, non-fluorine polymers, non-fluorine water and oil repellents, water-soluble polymer resins (e.g., hydrophilic polyesters and their derivatives, hydrophilic polyethylene glycols and their derivatives, hydrophilic polyamines and their derivatives, hydrophilic polyvinyl alcohols and their derivatives), crosslinking agents, penetrants (e.g., nonionic surfactants having a symmetrical structure with an acetylene group in the center, the Dispanol (registered trademark) series manufactured by NOF Corporation), colloidal silica (e.g., the Snowtex (registered trademark) series manufactured by Nissan Chemical Industries, Ltd., the Adelite series manufactured by ADEKA Corporation), antifoaming agents (e.g., the Orfin (registered trademark) series manufactured by Nissin Chemical Industry Co., Ltd., the FS Antifoam series manufactured by Toray Dow Corning Co., Ltd.), film-forming aids, insect repellents, fungicides, preservatives, flame retardants, antistatic agents (e.g., the Director series manufactured by Meisei Chemical Works, Ltd.), anti-wrinkle agents, softeners (e.g., silicone emulsions, polyethylene wax emulsions, polyamide wax emulsions), pH adjusters (e.g., diethanolamine, triethanolamine, acetic acid, citric acid), fatty acid amides (e.g., those described in Japanese Patent Application Laid-Open No. 2014-98082), acrylic resins, and urethane resins. Two or more of these may be used in combination. From the viewpoint of suppressing outgassing from the article, it is preferable that the other components do not contain volatile components that can volatilize at the treatment temperature when treating the article.

[0040] When the composition contains a medium, the content of the medium can be appropriately selected according to the desired solid content concentration of the composition. The solid content concentration of the composition is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, immediately after the composition is produced. When the composition is used for treating an article, the solid content concentration is preferably 0.1 to 7% by mass, more preferably 0.2 to 5% by mass.

[0041] When the composition contains a surfactant, the content of the surfactant is preferably 1 to 6 parts by mass with respect to 100 parts by mass of Polymer A. If the content of the surfactant is at least the above lower limit value, the composition has excellent dispersion stability. If the content of the surfactant is at most the above upper limit value, the adverse effects of the surfactant on the water and oil repellency, water pressure resistance, and water absorption rate of the article treated with the composition can be reduced.

[0042] A preferred embodiment of the composition is a fluorine-containing polymer dispersion liquid containing Polymer A, an aqueous medium, and a surfactant. The fluorine-containing polymer dispersion liquid includes the dispersion liquid obtained by the production method of the water and oil repellent composition described below, and the dispersion liquid diluted with an arbitrary medium for treating an article.

[0043] In the fluorine-containing polymer dispersion liquid, Polymer A is dispersed as emulsion particles in the aqueous medium. In the fluorine-containing polymer dispersion liquid, the average particle diameter of the emulsion particles of Polymer A is preferably 50 to 500 nm, more preferably 70 to 400 nm, and even more preferably 80 to 300 nm. If the average particle diameter is at most the above upper limit value, the article treated with the emulsion particles of Polymer A can have higher water pressure resistance and lower water absorption rate, and the dispersibility of the emulsion particles of Polymer A is more excellent. If the average particle diameter is at least the above lower limit value, the emulsion particles of Polymer A are more stable against mechanical shear. The average particle diameter of the emulsion particles of Polymer A is calculated by cumulant method analysis from the autocorrelation function obtained by dynamic light scattering method for a sample in which the dispersion liquid of Polymer A is diluted with water to a solid content concentration of 1 mass%.

[0044] 〔Method for producing water and oil repellent composition〕 The method for producing the water and oil repellent composition of the present invention (hereinafter, also referred to as "this production method") is a method of polymerizing a monomer component in the presence of a polymerization initiator to obtain a water and oil repellent composition containing Polymer A.

[0045] The monomer component includes monomer (a), monomer (b1), monomer (b2), monomer (b3), and monomer (c), and may further include other monomers. The monomer (a), monomer (b1), monomer (b2), monomer (b3), monomer (c), and other monomers are as described above.

[0046] The proportion of monomer (a) in the total monomer components is 70 to 80% by mass, preferably 72 to 78% by mass. If the proportion of monomer (a) is within the above range, an article treated with the water and oil repellent composition obtained by the present production method can have high water pressure resistance and low water absorption.

[0047] The total proportion of monomer (b1), monomer (b2), and monomer (b3) in the total monomer components is 12 to 28% by mass, preferably 14 to 26% by mass, and may be 14 to 25% by mass. If the total proportion of monomer (b1), monomer (b2), and monomer (b3) is within the above range, an article treated with the present composition can have high water pressure resistance and low water absorption.

[0048] The proportion of monomer (b1) in the total of monomer (b1), monomer (b2), and monomer (b3) is preferably 60 to 80% by mass, more preferably 64 to 76% by mass. The proportion of monomer (b2) in the total of monomer (b1), monomer (b2), and monomer (b3) is preferably 10 to 20% by mass, more preferably 12 to 18% by mass. The proportion of monomer (b3) in the total of monomer (b1), monomer (b2), and monomer (b3) is preferably 10 to 20% by mass, more preferably 12 to 18% by mass. If the proportions of monomer (b1), monomer (b2), and monomer (b3) are within the above ranges, an article treated with the present composition can have even higher water pressure resistance and lower water absorption. With respect to the total of monomer (b1), monomer (b2), and monomer (b3), the proportion of monomer (b1) is preferably 60 to 80% by mass, the proportion of monomer (b2) is preferably 10 to 20% by mass, and the proportion of monomer (b3) is preferably 10 to 20% by mass. More preferably, the proportion of monomer (b1) is 64 to 76% by mass, the proportion of monomer (b2) is 12 to 18% by mass, and the proportion of monomer (b3) is 12 to 18% by mass. If the proportions of monomer (b1), monomer (b2), and monomer (b3) are within the above ranges, the article treated with this composition can have higher water pressure resistance and lower water absorption rate.

[0049] The proportion of monomer (c) with respect to the total monomer component is 2 to 8% by mass, preferably 2 to 7% by mass, and may be 3 to 7% by mass. If the proportion of monomer (c) is at least the above lower limit value, the adhesion to the substrate of polymer A is excellent, and if it is at most the above upper limit value, the article treated with this composition can have higher water pressure resistance and lower water absorption rate.

[0050] Examples of the polymerization initiator include, for example, thermal polymerization initiators, photo polymerization initiators, radiation polymerization initiators, radical polymerization initiators, and ionic polymerization initiators, and radical polymerization initiators are preferred. As the radical polymerization initiator, for example, azo-based polymerization initiators, peroxide-based polymerization initiators, and redox-based initiators are used according to the polymerization temperature. As the radical polymerization initiator, azo-based compounds are preferred, and salts of azo-based compounds are more preferred. The polymerization temperature is preferably 20 to 150°C. The addition amount of the polymerization initiator is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the monomer component.

[0051] When polymerizing the monomer component, a molecular weight regulator may be used. As the molecular weight regulator, for example, aromatic compounds, mercapto alcohols, mercapto carboxylic acids, and alkyl mercaptans are preferred, and mercapto carboxylic acids or alkyl mercaptans are more preferred. Examples of the molecular weight regulator include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, and α-methylstyrene dimer (CH2=C(Ph)CH2C(CH3)2Ph, where Ph is a phenyl group). The addition amount of the molecular weight regulator is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and may even be 0 parts by mass with respect to 100 parts by mass of the monomer component.

[0052] Examples of the polymerization method of the monomer component include emulsion polymerization method, solution polymerization method, suspension polymerization method, and bulk polymerization method. Among these, the emulsion polymerization method is preferred. By polymerizing the monomer component by the emulsion polymerization method, the conversion rate of the monomer component to the polymer A can be improved without using a medium other than the aqueous medium, and the molecular weight (Mn, Mw) of the polymer A can be increased.

[0053] In the emulsion polymerization method, for example, the monomer component is polymerized in an aqueous medium in the presence of a polymerization initiator and a surfactant. The surfactant and the aqueous medium are as described above. To polymerize the monomer component in an aqueous medium in the presence of a polymerization initiator and a surfactant, first, an emulsion containing an aqueous medium, a monomer component, a polymerization initiator, and a surfactant is prepared. The emulsion may contain a molecular weight regulator as necessary.

[0054] The emulsion can be prepared by mixing an aqueous medium, a monomer component, and, if necessary, a surfactant, dispersing them with a homogenizer, a high-pressure emulsifier, etc., and then adding a polymerization initiator. The concentration of the monomer component in the emulsion is preferably 20 to 60% by mass, more preferably 30 to 50% by mass. If the concentration of the monomer component in the emulsion is within the above range, the conversion rate of the monomer component to the polymer A during the polymerization of the monomer component can be improved, and the molecular weight of the polymer A can be made sufficiently high.

[0055] In the emulsion, the content of the surfactant is preferably 1 to 6 parts by mass with respect to 100 parts by mass of the monomer component. If the content of the surfactant is at least the above lower limit value, the emulsion has excellent dispersion stability. If the content of the surfactant is at most the above upper limit value, the adverse effects on the water and oil repellency, water pressure resistance, and water absorption rate of the article treated with the composition containing the polymer A caused by the surfactant can be reduced.

[0056] By polymerizing the monomer component in the emulsion, a dispersion of the polymer A can be obtained. The polymerization temperature is, for example, 20 to 90°C. The conversion rate of the monomer component to the polymer A at the end of the polymerization is preferably 80% or more, more preferably 90% or more. By increasing the conversion rate, the molecular weight of the polymer A also increases, and the water and oil repellency becomes good. Also, by achieving a high conversion rate, the performance degradation due to the residual monomer is suppressed, and the amount of fluorine atoms contained in the polymer A increases, so the water and oil repellency becomes good. To make the conversion rate 80% or more, it is preferable to optimize the emulsion composition and the polymerization time. The obtained dispersion may be used as the composition as it is, or may be diluted with a medium to adjust the solid content concentration to obtain the composition. Other components may be further added to the composition.

[0057] 〔Article〕 The article of the present invention is an article treated with the composition. Examples of articles to be treated with the present composition (hereinafter also referred to as "substrate") include, for example, fibers, fibrous fabrics (fiber weaves, fiber knits, non-woven fabrics, flannel fabrics, etc.), fiber products provided with fibrous fabrics (clothes such as key wear, rainwear, coats, blousons, windbreakers, down jackets, sportswear, work clothes, uniforms, protective clothing, etc.), rucksacks, backpacks, bags, tents, tepees, etc.), glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, porous resins, and porous fibers.

[0058] The type of fiber is not particularly limited, and examples thereof include natural fibers such as cotton, wool, silk or cellulose, synthetic fibers such as polyester, polyamide, acrylic or aramid, chemical fibers such as rayon, viscose rayon or lyocell, blended fibers of natural fibers and synthetic fibers, and blended fibers of natural fibers and chemical fibers. Examples of fibers in the case where the fibrous fabric is a non-woven fabric include polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass, and rayon. The thickness of the fibrous fabric is not particularly limited, but is usually 0.01 to 5 mm. Examples of the material of the porous resin include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene. Examples of the material of the porous fiber include glass fiber, cellulose nanofiber, carbon fiber, and cellulose acetate.

[0059] A preferred embodiment of the article of the present invention is an air filter in which the filter medium is treated with the present composition. Examples of the material of the filter medium include glass fiber, polyolefin fiber, natural fiber, and polytetrafluoroethylene fiber. Glass fiber is preferred for clean rooms. The form of the filter medium made of glass fiber is preferably a non-woven fabric.

[0060] (Method for manufacturing an article) The article of the present invention is manufactured by treating a substrate with the present composition. As a treatment method, any method that can attach the present composition to a substrate may be used. For example, when the present composition contains a medium, after attaching the present composition to the substrate by a known coating method such as coating, impregnation, dipping, spraying, brushing, padding, size press, roller, etc., a method of drying may be mentioned. When the substrate is a non-woven fabric, a method of attaching the present composition in the molding process of the non-woven fabric may also be used. When the substrate is a wet non-woven fabric (wet laid), a method of adding the present composition to a suspension of the fibers constituting the non-woven fabric to attach it to the substrate and then drying may also be used. As a treatment method when the substrate is a filter medium, a method of dipping the filter medium in a treatment liquid containing the present composition and then drying is preferable. The treatment liquid is prepared by diluting the present composition with a dilution medium as necessary and then blending a co-agent as necessary. As the dilution medium, water is preferable. Examples of the co-agent include an anionic acrylic resin, a fluorine-based surfactant, and a non-fluorine-based surfactant. The solid content concentration of the treatment liquid is preferably 0.2 to 5% by mass. The amount of the solid content in the water and oil repellent composition to be attached to the substrate is not particularly limited. For example, in the case of a fiber fabric, it is preferably 0.001 to 0.05 g / g based on the unit mass of the fiber fabric. Drying may be performed at room temperature or by heating, and heating is preferable. When heating, the heating temperature is preferably 40 to 200°C. Further, when the present composition contains a crosslinking agent, if necessary, it is preferable to heat to a temperature equal to or higher than the crosslinking temperature of the crosslinking agent for curing.

Examples

[0061] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Room temperature is 20 ± 10°C. "Parts" means "parts by mass". Examples 1 to 5 are examples, and Examples 6 to 12 are comparative examples.

[0062] (Molecular weight) <Recovery of fluorine-containing polymer> 6 g of the fluorine-containing polymer dispersion was dropped into 60 g of a mixed solution of 54 g of 2-butanol and 6 g of hexane, and stirred to precipitate a solid. After centrifuging at 3000 rpm for 5 minutes, the obtained solid was separated. 9 g of isopropyl alcohol and 21 g of ion-exchanged water were added to the separated solid and stirred well. After centrifuging at 3000 rpm for 5 minutes, the obtained solid was separated from the supernatant and vacuum-dried at 35 °C overnight to obtain a fluorine-containing polymer.

[0063] <Measurement of Mn and Mw> The recovered fluorine-containing polymer was dissolved in a mixed solvent of a fluorine-based solvent (manufactured by AGC, AK-225) / tetrahydrofuran = 6 / 4 (volume ratio) to form a solution with a solid content concentration of 1% by mass, passed through a 0.2-μm filter, and used as an analysis sample. For the analysis sample, Mn and Mw were measured by GPC measurement. The measurement conditions are as follows. Apparatus: HLC-8220GPC manufactured by Tosoh Corporation Column: A combination of MIXED-C and 100A manufactured by Polymer laboratories in series Mobile phase: A mixed solvent of a fluorine-based solvent (manufactured by AGC, AK-225) / tetrahydrofuran = 6 / 4 (volume ratio) Flow rate: 1 mL / min Oven temperature: 37 °C Sample concentration: 1% by mass Injection volume: 50 μL Detector: RI Molecular weight standard: Polymethyl methacrylate

[0064] (Average particle size) For a diluted solution obtained by diluting the fluorine-containing polymer dispersion with water so that the solid content concentration becomes 1% by mass, at 25 ± 2 °C, using a dynamic light scattering photometer (product name of Otsuka Electronics Co., Ltd., ELS-Z2), the scattering intensity was measured, and the average particle size of the emulsion particles of the fluorine-containing polymer was measured by analyzing from the obtained autocorrelation function by the cumulant method.

[0065] (Compatibility) A treatment liquid prepared by diluting a fluorine-containing polymer dispersion with water to a solid content concentration of 0.5% by mass and an anionic acrylic resin (manufactured by DIC Corporation, Dick Fine GM-3K) were mixed so that the solid content ratio was 1:1, allowed to stand at room temperature for 60 minutes, and then the occurrence of sedimentation was visually observed. ○: No sedimentation at all. △: Slight sedimentation. ×: Considerable sedimentation.

[0066] (Water resistance pressure) For the air filter, by measuring the water resistance according to JIS L 1092, under the condition of a pressure increase rate of 60 mbar / min, the pressure at which three water droplets passed through or the pressure at which the air filter broke was defined as the water resistance pressure. The water resistance pressure is preferably 200 mmH2O or more.

[0067] (Water absorption rate) The water absorption rate was calculated by the following formula from the mass change of the air filter before and after the water resistance pressure measurement. The water absorption rate is preferably less than 60%. Water absorption rate (%) = (mass of the air filter after water resistance pressure measurement (g) - mass of the air filter before water resistance pressure measurement (g)) / mass of the air filter before water resistance pressure measurement (g) × 100

[0068] (Outgas) Measurement was performed by the headspace GC-MS method, and the amount of the generated volatile components (outgas) was evaluated according to the following criteria. Evaluation criteria: 〇: Less than 1000 ppm of outgas components ×: 1000 ppm or more of outgas components The analysis conditions of the headspace GC-MS method are as follows. Apparatus: Agilent7697A (headspace sampler), Agilent7890B (GC system), Agilent5977MSD (MS system) (all from Agilent Technologies, Inc.) Headspace conditions: Heating temperature: 80 °C Heating time: 60 minutes Loop volume: 1 mL GC conditions: Column: VF-1301 (length 60 m, inner diameter 0.25 mm, film thickness 1 μm) Flow rate: Helium 1.0 mL / min Vaporization chamber temperature: 250 °C Oven temperature: Held at 40 °C for 5 minutes, then heated at 10 °C / min, then held at 260 °C for 13 minutes, then heated at 10 °C / min, then held at 280 °C for 5 minutes. Split ratio: 25 / 1 MS conditions: Transfer line temperature: 250 °C Ion source temperature: 230 °C Ionization method: EI Scan range: 10 - 700

[0069] (Monomer) C6FMA: CH2=C(CH3)C(O)O-(CH2)2-(CF2)6F BeMA: Behenyl methacrylate (alkyl group has 22 carbon atoms) C20MA: Arachidyl methacrylate (alkyl group has 20 carbon atoms) StMA: Stearyl methacrylate (alkyl group has 18 carbon atoms) LMA: Lauryl methacrylate (alkyl group has 12 carbon atoms) BeMA-70: A mixture of 70 mass% BeMA, 15 mass% C20MA, and 15 mass% StMA VCM: Vinyl chloride DOM: Dioctyl maleate

[0070] The ratio (mass%) of each monomer in BeMA-70 was calculated from the area ratio of the peaks of each monomer by analyzing BeMA-70 by gas chromatography. The analysis conditions for gas chromatography are as follows. Equipment: HP-6850, manufactured by Agilent Column: DB-1, manufactured by Agilent J&W (inner diameter 0.25 mm, film thickness 1 μm, length 60 m) Injection volume: 1 μL Injection temperature: 325 °C Detection temperature: 325 °C Oven temperature: It was maintained at 40 °C for 5 minutes and then heated at a rate of 20 °C / min, and then maintained at 325 °C for 20 minutes. Detector: FID Split ratio: 100 / 1

[0071] (Nonionic surfactant) SFY465: Acetylene glycol ethylene oxide adduct (manufactured by Nissin Chemical Industry Co., Ltd., Surfynol 465, number of moles of ethylene oxide added: 10) E430: Polyoxyethylene oleyl ether (manufactured by Kao Corporation, Emulgen 430, adduct of about 30 moles of ethylene oxide) (Cationic surfactant) AQ18: Aqueous solution containing 32% by mass of isopropyl alcohol and 63% by mass of stearyltrimethylammonium chloride (manufactured by Lion Specialty Chemical Co., Ltd., Lipgard 18-63)

[0072] (Polymerization initiator) V-601: Dimethyl 2,2’-azobis(2-methylpropionate) (Molecular weight regulator) n-DoSH: Normal dodecyl mercaptan (Medium) Water: Ion-exchanged water DPG: Dipropylene glycol (boiling point at atmospheric pressure: 232 °C)

[0073] (Examples 1 to 12) A glass autoclave was charged with the monomers shown in Table 1 (excluding VCM), a surfactant (where AQ18 indicates the amount of the active ingredient), a molecular weight regulator, and a medium. After heating at 55 °C for 60 minutes, it was pretreated at 10 MPa using a high-pressure emulsifier (manufactured by Nippon Seiki Co., Ltd.) and then subjected to the main treatment at 50 MPa to obtain an emulsion. The resulting emulsion was placed in a stainless steel reactor and cooled to 30 °C or lower. A polymerization initiator shown in Table 1 was added thereto, the gas phase was replaced with nitrogen, and then the amount of VCM shown in Table 1 was introduced. Polymerization was carried out at 65 °C for 15 hours with stirring to obtain a fluoropolymer dispersion. Table 2 shows the monomer composition (the ratio of each monomer to the total monomer components), the solid content concentration of the fluoropolymer dispersion, the molecular weights (Mn and Mw) of the fluoropolymer, and the average particle diameter.

[0074] The obtained fluoropolymer dispersion was diluted with water so that the solid content concentration became 0.5 mass% to prepare a treatment liquid. The compatibility of the treatment liquid was evaluated. The results are shown in Table 2.

[0075] A glass fiber filter paper (manufactured by Advantec Toyo Kaisha, Ltd., GB-100R) was immersed in the above treatment liquid at room temperature for 3 minutes. Then, the glass fiber filter paper was taken out from the treatment liquid, sandwiched between absorbent papers, and excess treatment liquid was removed by placing a weight thereon to obtain a wet pickup of 600%. This glass fiber filter paper was heat-treated at 130 °C for 15 minutes to obtain a sample equivalent to an air filter. The water pressure resistance, water absorption rate, and outgas of the sample were evaluated. The results are shown in Table 2.

[0076]

Table 1

[0077]

Table 2

[0078] The samples treated with the treatment liquids of Examples 1 to 5 had higher water pressure resistance and lower water absorption rate than the samples treated with the treatment liquids of Examples 6 to 12. The treatment liquids of Examples 2 to 5 that do not contain a cationic surfactant were excellent in compatibility. The samples treated with the treatment liquids of Examples 3 to 5 that do not contain an organic solvent having a boiling point of 280°C or lower at atmospheric pressure had suppressed outgassing.

Industrial Applicability

[0079] Since the water- and oil-repellent agent composition of the present invention can provide an article having high water pressure resistance and low water absorption rate, it is used in applications that require these properties, such as air filters, oil filters, dust collection filters, cartridge filters, bag filters, filter papers, etc. In addition, the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2020-124144 filed on July 21, 2020 are hereby incorporated by reference and made a part of the disclosure of the specification of the present invention.

Claims

1. A water and oil repellent composition comprising a fluorine-containing polymer having units based on the following monomer (a), units based on the following monomer (b1), units based on the following monomer (b2), units based on the following monomer (b3), and units based on the following monomer (c), wherein, based on all the units constituting the fluorine-containing polymer, the proportion of the units based on the monomer (a) is 70 to 80% by mass, the total proportion of the units based on the monomer (b1), the units based on the monomer (b2), and the units based on the monomer (b3) is 12 to 28% by mass, and the proportion of the units based on the monomer (c) is 2 to 8% by mass. Monomer (a): (Z-Q) ｎ A compound represented by X. However, Z is a polyfluoroalkyl group having 1 to 6 carbon atoms, Q is a divalent organic group or a single bond, n is 1, X is a group represented by -CR=CH ２ or -OC(O)CR=CH2, and R is a hydrogen atom, a methyl group or a halogen atom. Monomer (b1): A monomer having no polyfluoroalkyl group and having an alkyl group with 22 carbon atoms. Monomer (b2): A monomer having no polyfluoroalkyl group and having an alkyl group with 20 carbon atoms. Monomer (b3): A monomer having no polyfluoroalkyl group and having an alkyl group with 18 carbon atoms. Monomer (c): A halogenated olefin.

2. Based on the total of the units based on the monomer (b1), the units based on the monomer (b2), and the units based on the monomer (b3), the proportion of the units based on the monomer (b1) is 60 to 80% by mass, the proportion of the units based on the monomer (b2) is 10 to 20% by mass, and the proportion of the units based on the monomer (b3) is 10 to 20% by mass. The water and oil repellent composition according to Claim 1.

3. The water and oil repellent composition according to Claim 1 or 2, wherein each of the monomer (b1), the monomer (b2), and the monomer (b3) is an acrylate or a methacrylate.

4. The water and oil repellent composition according to any one of Claims 1 to 3, wherein Z of the monomer (a) is a polyfluoroalkyl group having 6 carbon atoms.

5. The water and oil repellent composition according to any one of Claims 1 to 4, which does not contain a cationic surfactant.

6. The water and oil repellent composition according to any one of Claims 1 to 5, which does not contain an organic solvent having a boiling point of 280 °C or lower at atmospheric pressure.

7. A method for obtaining a water and oil repellent composition containing a fluorine-containing polymer by polymerizing a monomer component in the presence of a polymerization initiator, wherein the monomer component contains the following monomer (a), the following monomer (b1), the following monomer (b2), the following monomer (b3), and the following monomer (c). A method for producing a water and oil repellent composition, wherein the proportion of the monomer (a) is 70 to 80% by mass, the total proportion of the monomer (b1), the monomer (b2), and the monomer (b3) is 12 to 28% by mass, and the proportion of the monomer (c) is 2 to 8% by mass with respect to the total monomer components. Monomer (a): (Z-Q) ｎ A compound represented by X. However, Z is a polyfluoroalkyl group having 1 to 6 carbon atoms, Q is a divalent organic group or a single bond, n is 1, X is a group represented by -CR=CH ２ or -OC(O)CR=CH2, and R is a hydrogen atom, a methyl group or a halogen atom. Monomer (b1): A monomer having no polyfluoroalkyl group and having an alkyl group with 22 carbon atoms. Monomer (b2): A monomer having no polyfluoroalkyl group and having an alkyl group with 20 carbon atoms. Monomer (b3): A monomer having no polyfluoroalkyl group and having an alkyl group with 18 carbon atoms. Monomer (c): A halogenated olefin.

8. A method for producing a water and oil repellent composition according to claim 7, wherein the proportion of the monomer (b1) is 60 to 80% by mass, the proportion of the monomer (b2) is 10 to 20% by mass, and the proportion of the monomer (b3) is 10 to 20% by mass with respect to the total of the monomer (b1), the monomer (b2), and the monomer (b3).

9. A method for producing a water and oil repellent composition according to claim 7 or 8, wherein each of the monomer (b1), the monomer (b2), and the monomer (b3) is an acrylate or a methacrylate.

10. A method for producing a water and oil repellent composition according to any one of claims 7 to 9, wherein the monomer components are polymerized in a medium containing water in the presence of the polymerization initiator and the surfactant.

11. A method for producing a water and oil repellent composition according to claim 10, wherein the surfactant does not contain a cationic surfactant.

12. A method for producing a water and oil repellent composition according to claim 10 or 11, wherein the medium does not contain an organic solvent having a boiling point of 280 ° C or lower at atmospheric pressure.

13. An article treated with the water and oil repellent composition according to any one of claims 1 to 6.

14. The article according to claim 13, which is an air filter.

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