dispersion

Abstract

DEPCT66 The provided product is a dispersant that possesses both product stability and water-repellent properties and / or The oil-repellent condition is combined with a fluorine-containing polymer and a liquid medium in which: polymer Containing fluorine with a Q value of at least 2.0 and having repeating units derived from fluorine-containing monomers (a) with a group Fluoroalkyl and repeat units derived from chloride monomers (b) at least one of which are selected. Types from among vinyl chloride and vinylidine chloride; and concentrations of chloride monomers. Non-reactive(b) is at most 2.0 parts per million. -----------------------------------------------------------

Description

dispersion liquid This disclosure relates to a dispersion. It is known that by using a water-dispersible water- and oil-repellent agent comprising a copolymer obtained by copolymerizing a polyfluoroalkyl group-containing monomer, vinyl chloride or vinylidene chloride, and other copolymerizable monomers, and having a concentration of unreacted vinyl chloride monomer or vinylidene chloride monomer of 10 ppm or less, it is possible to provide a water- and oil-repellent agent with excellent storage stability that reduces problems such as changes in the form of the water- and oil-repellent agent and deterioration of its performance (Patent Document 1). Japanese Unexamined Patent Publication No. 4-80218 However, when using fluorine-containing polymers other than those described in Patent Document 1, product stability and water and / or oil repellency are insufficient. The object of this disclosure is to provide a novel dispersion that can achieve both product stability and water and / or oil repellency. One embodiment of this disclosure is as follows: [Section 1] A dispersion comprising a fluorine-containing polymer and a liquid medium, Fluorine-containing polymers A fluorine-containing monomer (a) having a Q value of 2.0 or higher and containing a fluoroalkyl group. Repeating units derived from, and (b) Chloride monomers, at least one selected from vinyl chloride and vinylidene chloride. Repeating units derived from A dispersion containing the above, wherein the concentration of unreacted chloride monomer (b) is 2.0 ppm or less. [Section 2] Fluorine-containing monomer (a) is given by formula: CH ２ =C(-X)-C(=O)-Y-Z-Rf [In the formula, X is a halogen atom, Y is -O- or -NH-, Z is either a direct bond or a divalent organic group. Rf is a fluoroalkyl group having 1 to 20 carbon atoms. The dispersion described in item 1, which is the compound shown by [the specified compound]. [Section 3] The dispersion described in item 2, wherein X is a chlorine atom. [Section 4] The dispersion according to item 2 or 3, wherein Rf is a perfluoroalkyl group having 3 to 6 carbon atoms. [Section 5] The dispersion according to any one of claims 1 to 4, wherein the amount of repeating units derived from the chloride monomer (b) is less than 25% by weight relative to the fluorine-containing polymer. [Section 6] Fluorine-containing polymers formula: CH ２ =CA ２１ -C(=O)-O-A ２２ [In the formula, A ２１ A is a hydrogen atom, a monovalent organic group, or a halogen atom. ２２ This is a hydrocarbon group having 2 to 40 carbon atoms. hydrocarbon group-containing monomer (c) A dispersion according to any one of claims 1 to 5, further comprising repeating units derived from. [Section 7] Fluorine-containing polymers A 22 C1 is a monomer containing a long-chain hydrocarbon group, which is an acyclic aliphatic hydrocarbon group having 12 to 30 carbon atoms. The dispersion according to item 6, comprising repeating units derived from. [Section 8] The dispersion according to claim 6 or 7, wherein the total amount of repeating units derived from the fluorine-containing monomer (a), the chloride monomer (b), and the hydrocarbon group-containing monomer (c) is 90% by weight or more relative to the fluorine-containing polymer. [Section 9] Fluorine-containing polymers A crosslinkable monomer (d) having at least two selected from the group consisting of a reactive group and an olefinic carbon-carbon double bond. A dispersion according to any one of claims 1 to 8, further comprising repeating units derived from. [Section 10] The dispersion according to claim 9, wherein the repeating units derived from the fluorine-containing monomer (a) are 25% by weight or more relative to the fluorine-containing polymer, and the repeating units derived from the crosslinkable monomer (d) are 10% by weight or less relative to the fluorine-containing polymer. [Section 11] A dispersion according to any one of items 1 to 10, wherein the concentration of unreacted chloride monomer (b) is 1.0 ppm or less. [Section 12] A dispersion according to any one of claims 1 to 11, wherein the liquid medium contains at least 30% by weight of water. [Section 13] Step (i) involves copolymerizing a fluorine-containing monomer (a) containing a fluoroalkyl group and having a Q value of 2.0 or higher in the Q-e scheme, and a chloride monomer (b) which is at least one selected from vinyl chloride and vinylidene chloride, in a liquid medium to obtain a polymerization solution containing a fluorine-containing polymer, and (ii) A step to reduce the concentration of unreacted chloride monomer (b) in the obtained polymerization solution to 2.0 ppm or less. A method for producing a dispersion containing [the specified ingredient]. [Section 14] A method for producing a product to be treated, comprising the step of applying a dispersion liquid described in any of items 1 to 12 to a substrate. The dispersion in this disclosure exhibits excellent product stability and water- and oil-repellent properties. <Dispersion> Dispersions (especially aqueous dispersions) Fluorine-containing polymers, and liquid medium The dispersion further comprises the following: Surfactants, and / or hardening agent It may contain [the specified ingredient]. The dispersion may contain other components. [Fluorine-containing polymer] Fluorine-containing polymers are Fluorine-containing monomer (a) Repeating units derived from, and Chloride monomer (b) It contains repeating units derived from. Fluorine-containing polymers further A hydrocarbon group-containing monomer (c) and / or A crosslinkable monomer (d) may be included. The fluorine-containing polymer may also contain other monomers (e). (Fluorine-containing monomer (a)) The fluorine-containing polymer has a Q value of 2.0 or more and contains a repeating unit derived from a fluorine-containing monomer (a) containing a fluoroalkyl group. The Q value of the fluorine-containing monomer (a) may be 2.0 or more, 2.2 or more, 2.4 or more, 2.6 or more, or 2.8 or more, preferably 2.6 or more or 2.8 or more. The Q value of the fluorine-containing monomer (a) may be 10.0 or less, 8.0 or less, 6.0 or less, 4.0 or less, 3.5 or less, or 3.0 or less, preferably 3.5 or less or 3.0 or less. The e value of the fluorine-containing monomer (a) may be 0.6 or more, 0.8 or more, 0.9 or more, or 1.0 or more, preferably 0.9 or more or 1.0 or more. The e value of the fluorine-containing monomer (a) may be 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, or 1.1 or less, preferably 1.3 or less, 1.2 or less, or 1.1 or less. In the above, the Q value is an index representing the degree of resonance stabilization effect between the double bond of the radically polymerizable monomer and its substituent. Also, the e value of the monomer is an index representing the degree of polarity of the double bond of the radically polymerizable monomer. With styrene as the reference (Q value = 1.0, e value = -0.8), the Q values and e values for various monomers have been experimentally determined. The Q values and e values of representative monomers are described in "Polymer Handbook Fourth Edition" by J. Brandrup, E. H. Immergut, E. A. Grulke (John Wiley & Sons Inc., 1998), etc. These values may be referred to, or they may be calculated according to the following "Calculation method of Q-e values". Calculation method of Q-e values 1) Calculation of monomer reactivity ratio Generally, the reactivity ratios (r of the monomers for estimating the composition of the copolymer １ , r ２) is shown in the following equation: Mayo-Lewis １） The result is obtained using equation [1], followed by the Fineman-Ross method. ２） It is generally obtained from the linearized equation [2]. When two monomers are copolymerized, each monomer M1, M2, ~M1•, ~M2• exhibits radical behavior, and the reaction rate constant k of the four growth reactions １１ , k １２ , k ２２ , k ２１ If we set it as follows, it can be shown by the following equation. If we let the amount of monomer added be [M1] and [M2], and the amount of monomer decreased be d[M1] and d[M2], then the following equation is obtained. In equation [1] By setting this and transforming it into the Fineman-Ross formula, we derive equation [2]. From the graph obtained by plotting F{(f-1) / f} against {F(2 / f)} and approximating it with a straight line, r １ and r ２ This can be determined using the nonlinear least squares method. ３） Apply Δf ２ The sum of r is minimized １ and r ２ The combinations can also be calculated by applying the software's solver function. 2) Calculation of Q-e value ４） Reactivity ratio of monomers in radical copolymerization (r １ ,r ２ The growth reaction rate constant k of radical copolymerization is determined by the monomer structure and is considered to be unaffected by temperature, pressure, solvent, etc. Generally, the monomer structure effect on the relative rate of the growth reaction can be expressed by resonance and polar effects when steric effects are negligible. Alfrrey and Price have given the growth reaction rate constant k of radical copolymerization shown in equation [3]. 12 We assumed that it is expressed by equation [4]. 5） . P １ M １ • General reactivity, Q ２M ２ Resonance stabilization effect of monomers, e １ , e ２ Each is M １ M ２ This shows the polarity effect. Equation [4] shows the monomer reaction ratio r of radical copolymerization. １ = k １１ / k １２ ,r ２ = k ２２ / k ２１ Substituting these values ​​into the equation yields equations [5] and [6]. Styrene is used as the reference monomer, with a Q value of 1.0 and an e value of -0.8. The e values ​​of the monomer and its radical are assumed to be equal. The monomer reactivity ratio (r) is calculated from the copolymerization of styrene with various fluorine-containing monomers. １ ,r ２ By substituting ) into equations [5] and [6], the Q and e values ​​of the fluorine-containing monomer (a) can be calculated. References: 1) FR Mayo, FM Lewis, J. Am. Chem. Soc., 1944, 66, 1594. 2) M. Fineman and SD Ross, J. Polym. Sci., 1950, 5, 259. 3) PW Tidwell, GA Mortimer, J. Polymer. Sci., 1965, A3, 369. 4) T. Otsu, in Progress in Polymer Science Japan, ed. by M. Imoto, S. Onogi, Kodansha Ltd., Tokyo, 1970, Vol.1, pp.4 5) T. Alfrey Jr., CC Price, J. Polym. Sci., 1947, 2. 101. Fluorine-containing monomer (a) is a fluorine-containing monomer containing a fluoroalkyl group. Fluorine-containing monomer (a) is generally a polymerizable compound having a perfluoroalkyl group or perfluoroalkenyl group and a (meth)acryloyl group or an α-substituted acryloyl group. In this specification, unless expressly indicated, the term "acrylic" includes not only compounds where the α-position is a hydrogen atom, but also compounds where the α-position is substituted with another group (e.g., a monovalent organic group including a methyl group or a halogen atom). In this specification, "(meth)acryloyl" means acryloyl or methacryloyl, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylamide" means acrylamide or methacrylamide. The fluorine-containing monomer (a) preferably has a halogen atom at the α-position, and its formula is: CH ２ =C(-X)-C(=O)-Y-Z-Rf [In the formula, X is a halogen atom, Y is -O- or -NH-, Z is either a direct bond or a divalent organic group. Rf is a fluoroalkyl group having 1 to 20 carbon atoms. It is preferable that the compound is one shown in [the formula]. X is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom. Y is preferably -O-. Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cyclic aliphatic group having 6 to 18 carbon atoms. Formula-R ２ (R １ ) N-SO ２ - or -R ２ (R １ ) A group represented by N-CO- (wherein R １ R is an alkyl group having 1 to 10 carbon atoms. ２ This is a linear alkylene group or a branched alkylene group having 1 to 10 carbon atoms. (Formula -CH) ２ CH(OR ３ )CH ２- (Ar-O) p - (wherein, R ３ (wherein is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (e.g., formyl or acetyl), Ar is an arylene group having substituents as needed, and p represents 0 or 1.) A group represented by formula - (CH ２ ) ｒ -Ar-(O) ｑ A group represented by - (wherein Ar is an arylene group optionally having substituents, q is 0 or 1, and r is 0 to 10), or a group represented by the formula - (CH ２ ) ｍ -SO ２ - (CH ２ ) ｎ - or - (CH ２ ) ｍ -S-(CH ２ ) ｎ The group may be represented by - (wherein m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, for example 1 or 2). The aromatic group or cyclic aliphatic group may be substituted or unsubstituted. S group or SO ２ The group may be directly bonded to the Rf group. Rf is preferably a perfluoroalkyl group. The number of carbon atoms in Rf may be 1 to 12, 1 to 8, 1 to 6, 3 to 6, 4 to 6, or 6, preferably 3 to 6, more preferably 4 to 6, and particularly preferably 6. Examples of Rf groups include -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -CF2CF2CF2CF3, -CF2CF(CF3)2, -C(CF ３ )3, -(CF2)4CF3, -(CF2)2CF(CF3)2, -CF2C(CF3)3, -CF(CF3)CF2CF2CF3, -(CF2)5CF3, -(CF2)3CF(CF3)2, -(CF2)4CF(CF3)2, -C8F 17 These are some examples. Specific examples of monomer (a) include, but are not limited to, the following. These may be used individually or in combination of two or more types. CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-S-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-Cl)-C(=O)-NH-(CH2)2-Rf [Rf is a fluoroalkyl group with a value between 1 and 20.] As monomer (a) CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf That is particularly preferable. (Chloride monomer (b)) The fluorine-containing polymer contains repeating units derived from a chloride monomer (b), which is at least one selected from vinyl chloride and vinylidene chloride. Preferably, the chloride monomer (b) is vinyl chloride. (Hydrogen group-containing monomer (c)) Fluorine-containing polymers CH ２ =CA ２１ -C(=O)-O-A ２２ Formula (c) [In formula (c), A ２１ A is a hydrogen atom, a monovalent organic group, or a halogen atom. ２２ This is a hydrocarbon group having 2 to 40 carbon atoms. hydrocarbon group-containing monomer (c) It may have repeating units derived from A. ２１ It is preferable that this is a hydrogen atom, a methyl group, or a chlorine atom. A ２２The (hydrocarbon group) may be an acyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms, or a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms. The number of carbon atoms in the acyclic aliphatic hydrocarbon group is preferably 12 to 30, more preferably 18 to 25. Specific examples of acyclic aliphatic hydrocarbon groups are lauryl, cetyl, stearyl, and behenyl. Specific examples of cyclic hydrocarbon groups are cyclohexyl, t-butylcyclohexyl, isobornyl, dicyclopentanyl, dicyclopentenyl, and adamantyl. Examples of linear or cyclic hydrocarbon groups having 1 to 30 carbon atoms include linear or branched saturated or unsaturated (e.g., ethylenically unsaturated) aliphatic hydrocarbon groups having 1 to 30 carbon atoms, saturated or unsaturated (e.g., ethylenically unsaturated) cyclic aliphatic groups having 4 to 30 carbon atoms, aromatic hydrocarbon groups having 6 to 30 carbon atoms, and aromatic aliphatic hydrocarbon groups having 7 to 30 carbon atoms. The hydrocarbon group-containing monomer (c) does not contain a polyfluoroalkyl group. The crosslinkable monomer (d) does not need to contain a fluorine atom. Examples include acrylate ester monomers having cyclic hydrocarbon-containing groups, such as cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate. These may be used alone or in combination of two or more types. (Long-chain hydrocarbon group-containing monomer (c1)) Fluorine-containing polymers In equation (c), A 22 A monomer containing a long-chain hydrocarbon group (c1) which is an acyclic aliphatic hydrocarbon group having 12 to 30 carbon atoms. It is preferable that it contains repeating units derived from. The 12 to 30 acyclic aliphatic hydrocarbon groups may be linear or branched, and are preferably linear. Specific examples of long-chain hydrocarbon group-containing monomers (c1) include acrylate ester monomers having acyclic aliphatic hydrocarbon groups, such as lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate. These may be used alone or in combination of two or more types. (Cyclic hydrocarbon group-containing monomer (c2)) In equation (c), A ２２ A monomer containing a cyclic hydrocarbon group (c2), where c2 is a cyclic hydrocarbon group. It is preferable to include repeating units derived from . Specific examples of cyclic hydrocarbon groups include cyclohexyl group-containing groups, t-butylcyclohexyl group-containing groups, isobornyl group-containing groups, dicyclopentanyl group-containing groups, dicyclopentenyl group-containing groups, adamantyl group-containing groups, and the like. Specific examples of cyclic hydrocarbon group-containing monomers (C2) include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate. These may be used individually or in combination of two or more types. (Cross-linkable monomer (d)) Fluorine-containing polymers A crosslinkable monomer (d) having at least two selected from the group consisting of a reactive group and an olefinic carbon-carbon double bond. It may have a repeating unit derived from. The crosslinkable monomer (d) may be a compound having at least two ethylenically unsaturated double bonds or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. The crosslinkable monomer (d) preferably has a (meth) acrylate group or a (meth) acrylamide group. Examples of the reactive group are a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, etc. The crosslinkable monomer (d) does not have a polyfluoroalkyl group. The crosslinkable monomer (d) may not have a fluorine atom. The crosslinkable monomer (d) has the formula: CH ２ =CE １ -C(=O)-E ２ -E ３ -E ４ [In the formula, E １ is a hydrogen atom, a methyl group or a halogen atom (for example, a chlorine atom, a bromine atom and an iodine atom), E ２ is -O- or -NH-, E ３ is an organic group having 1 to 20 carbon atoms, for example, a linear or branched aliphatic group having 1 to 20 carbon atoms (especially an alkylene group), for example, a group represented by the formula -(CH ２ ) ｘ -(where x is 1 to 10).), E ４ is a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group.] It may be a compound represented by. Specific examples of crosslinkable monomers include diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylamide, glycidyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. These may be used individually or in combination of two or more. (Other monomers (e)) Fluorine-containing polymers Other monomers (e) besides monomers (a) to (d) It may contain repeating units derived from. Specific examples of other monomers (b3) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and vinyl alkyl ethers. Other non-fluorinated monomers are not limited to these examples. These may be used alone or in combination of two or more types. (Composition of polymer) The amount of repeating units derived from the fluorine-containing monomer (a) may be 15% by weight or more, 25% by weight or more, 35% by weight or more, or 45% by weight or more, relative to the fluorine-containing polymer. The amount of repeating units derived from the fluorine-containing monomer (a) may be 90% by weight or less, for example, 80% by weight or less, 70% by weight or less, or 60% by weight or less, relative to the fluorine-containing polymer. The amount of repeating units derived from chloride monomer (b) may be 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more, relative to the fluorine-containing polymer. The amount of repeating units derived from chloride monomer (b) may be 45% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, or 22% by weight or less, relative to the fluorine-containing polymer, and preferably 25% by weight or less. The amount of repeating units derived from the hydrocarbon group-containing monomer (c) may be 5% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight or more, relative to the fluorine-containing polymer. The amount of repeating units derived from the hydrocarbon group-containing monomer (c) may be 45% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, or 22% by weight or less, relative to the fluorine-containing polymer. The amount of repeating units derived from the long-chain hydrocarbon group-containing monomer (c1) may be 5% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight or more, relative to the fluorine-containing polymer. The amount of repeating units derived from the long-chain hydrocarbon group-containing monomer (c1) may be 45% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, or 22% by weight or less, relative to the fluorine-containing polymer. The amount of repeating units derived from the crosslinkable monomer (d) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, relative to the fluorine-containing polymer. The amount of repeating units derived from the crosslinkable monomer (d) may be 15% by weight or less, 10% by weight or less, 7.5% by weight or less, or 5% by weight or less, relative to the fluorine-containing polymer. The amount of repeating units derived from other monomers (e) may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more, relative to the fluorine-containing polymer. The amount of repeating units derived from other monomers (e) may be 15% by weight or less, 10% by weight or less, or 5% by weight or less, relative to the fluorine-containing polymer. The amount of repeating units derived from the chloride monomer (b) may be 5 to 500 parts by weight, 10 to 200 parts by weight, 10 to 150 parts by weight, 15 to 200 parts by weight, 20 to 150 parts by weight, or 10 to 50 parts by weight per 100 parts by weight of repeating units derived from the fluorine monomer (a). The amount of repeating units derived from the hydrocarbon group-containing monomer (c) may be 5 to 500 parts by weight, 10 to 200 parts by weight, 10 to 150 parts by weight, 15 to 200 parts by weight, or 20 to 150 parts by weight per 100 parts by weight of repeating units derived from the fluorine-containing monomer (a). The amount of repeating units derived from the long-chain hydrocarbon group-containing monomer (c1) may be 5 to 500 parts by weight, 10 to 200 parts by weight, 10 to 150 parts by weight, 15 to 200 parts by weight, or 20 to 150 parts by weight per 100 parts by weight of repeating units derived from the fluorine-containing monomer (a). The amount of repeating units derived from the cyclic hydrocarbon group-containing monomer (c2) may be 5 to 500 parts by weight, 10 to 200 parts by weight, 10 to 150 parts by weight, 15 to 200 parts by weight, or 20 to 150 parts by weight per 100 parts by weight of repeating units derived from the fluorine-containing monomer (a). The amount of repeating units derived from the crosslinkable monomer (d) may be 1 to 50 parts by weight, 3 to 40 parts by weight, 3 to 30 parts by weight, 5 to 25 parts by weight, or 5 to 20 parts by weight per 100 parts by weight of repeating units derived from the fluorine-containing monomer (a). The amount of repeating units derived from other monomers (e) may be 1 to 50 parts by weight, 3 to 40 parts by weight, 3 to 30 parts by weight, 5 to 25 parts by weight, or 5 to 20 parts by weight per 100 parts by weight of repeating units derived from fluorine monomer (a). The total amount of repeating units derived from the fluorine-containing monomer (a), the chloride monomer (b), and the hydrocarbon group-containing monomer (c) may be 85% by weight or more, 90% by weight or more, or 95% by weight or more, relative to the fluorine-containing polymer. The total amount of repeating units derived from the fluorine-containing monomer (a), the chloride monomer (b), the hydrocarbon group-containing monomer (c), and the hydrocarbon group-containing monomer (d) may be 85% by weight or more, 90% by weight or more, or 95% by weight or more, relative to the fluorine-containing polymer. [Unreacted chloride monomer (b)] Unreacted chloride monomer (b) means at least one selected from vinyl chloride and vinylidene chloride. [Liquid media] The dispersion contains a liquid medium. The liquid medium may be an aqueous medium. The liquid medium may be water alone, an organic solvent alone, or a mixture of water and a (water-miscible) organic solvent. The amount of water may be 30% by weight or more, 50% by weight or more, or 80% by weight or more relative to the liquid medium. The amount of organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% or more) relative to the liquid medium. The liquid medium may be added after the fluorine-containing polymer has been produced by polymerization. For example, monomers are polymerized in the presence of an organic solvent to produce a fluorine-containing polymer, after which water is added and the organic solvent is removed by distillation. Removal of the organic solvent is not required. [Surfactants] The dispersion may contain a surfactant if it is an aqueous dispersion. The surfactant may include at least one of a nonionic surfactant, a cationic surfactant, and an anionic surfactant. Furthermore, the surfactant may also include an amphoteric surfactant. Alternatively, the dispersion may not contain a surfactant. Generally, the dispersion contains a surfactant if it is an aqueous dispersion. The surfactant may be added before or after polymerization, or it may not be added. Even without adding a surfactant, an aqueous dispersion in which a fluorine-containing polymer is dispersed in an aqueous medium can be obtained. Nonionic surfactants are nonionic surfactants having an oxyalkylene group. The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of a nonionic surfactant is generally preferably 2 to 100. Nonionic surfactants may be alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (which may be random copolymers or block copolymers) are preferred. Furthermore, nonionic surfactants are preferable because they do not contain aromatic groups due to environmental concerns (biodegradability, endocrine disruptors, etc.). Cationic surfactants may be amine salts, quaternary ammonium salts, or oxyethylene-added ammonium salts. Specific examples of cationic surfactants are not limited to alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt-type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and quaternary ammonium salt-type surfactants such as benzethonium chloride. Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride. Examples of anionic surfactants include fatty acid salts (where the fatty acid has, for example, 8 to 30 carbon atoms), sulfonates (for example, alkyl sulfonic acids, alkylbenzene sulfonates (where the alkyl group has, for example, 8 to 30 carbon atoms)), and sulfate esters (for example, alkyl sulfate esters (where the alkyl group has, for example, 8 to 30 carbon atoms)). Examples of anionic surfactants include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, sodium cocoyl sarcosinate, sodium N-cocoyl methyl taurate, sodium polyoxyethylene coconut alkyl ether sulfate, sodium dietherhexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, and sodium polyoxyethylene lauryl ether phosphate. Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyl dimethylaminoacetic acid betaine. Nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants may each be one type or a combination of two or more. The surfactant is preferably a nonionic surfactant and / or a cationic surfactant. A combination of a nonionic surfactant and a cationic surfactant is also acceptable. [Hardening agent] The dispersion may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound). The curing agent may also be added to the dispersion after the polymerization of the fluorine-containing polymer. To ensure good curing of the fluorine-containing polymer, the dispersion may contain a curing agent (crosslinking agent). Since non-fluorine crosslinkable (meth)acrylate or (meth)acrylamide monomers are active hydrogen-containing monomers or monomers containing active hydrogen-reactive groups, the fluorine-containing polymer has active hydrogen or active hydrogen-reactive groups. The curing agent is an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive groups of the fluorine-containing polymer. Examples of active hydrogen-reactive compounds include polyisocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds include hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds. The curing agent is preferably a polyisocyanate compound. Polyisocyanate compounds are compounds that have two or more isocyanate groups in a single molecule. Polyisocyanate compounds act as crosslinking agents. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate. These include aliphatic diisocyanates such as anatomethylcaproate, lysine ester triisocyanates, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanatomethylbenzene. Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are: These include m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate or mixtures thereof, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. Examples of polyisocyanate derivatives include various derivatives of the polyisocyanate compounds mentioned above, such as dimers, trimers, biuretes, allophanates, carbodiimides, uretodiones, uretoimines, isocyanurates, and iminooxadiazinediones. These polyisocyanates can be used individually or in combination of two or more types. It is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent, as the polyisocyanate compound. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in aqueous solutions and can be used in the same aqueous solution as the dispersion. Blocking agents sequester free isocyanate groups. Blocked polyisocyanate compounds can be easily reacted with hydroxyl groups by heating them to, for example, 100°C or higher, such as 130°C or higher, which regenerates the isocyanate groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. Polyisocyanate compounds can be used alone or in combination of two or more. Epoxy compounds are compounds that contain epoxy groups. Examples of epoxy compounds include epoxy compounds containing polyoxyalkylene groups, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound that has a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that have a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid. Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin. [Other ingredients] The dispersion may contain other components besides those listed above. Generally, other components are added after the fluorine-containing polymer has been produced. Examples of other components include non-fluorine water-repellent and / or oil-repellent compounds. (Non-fluorine water-repellent and / or oil-repellent compounds) The dispersion may contain water-repellent and / or oil-repellent compounds that do not contain fluorine atoms (non-fluorine water-repellent and / or oil-repellent compounds). The non-fluorinated water-repellent and / or oil-repellent compounds may be non-fluorinated acrylate polymers, saturated or unsaturated hydrocarbon compounds, or silicone compounds. Nonfluorinated acrylate polymers are homopolymers composed of one type of nonfluorinated acrylate monomer, copolymers composed of at least two types of nonfluorinated acrylate monomers, or copolymers composed of at least one type of nonfluorinated acrylate monomer and at least one other type of nonfluorinated monomer (ethylenically unsaturated compounds, such as ethylene and vinyl monomers). The non-fluorinated acrylate monomers that make up the non-fluorinated acrylate polymer are given by formula: CH ２ = CA-T [In the formula, A is a halogen atom other than a hydrogen atom, a methyl group, or a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom), T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms and possessing an ester bond. It is a compound represented by [the formula shown]. Examples of chain-like or cyclic hydrocarbon groups having 1 to 30 carbon atoms include straight-chain or branched aliphatic hydrocarbon groups having 1 to 30 carbon atoms, cyclic aliphatic groups having 4 to 30 carbon atoms, aromatic hydrocarbon groups having 6 to 30 carbon atoms, and aromatic aliphatic hydrocarbon groups having 7 to 30 carbon atoms. Examples of linear or cyclic organic groups having 1 to 31 carbon atoms and possessing ester bonds include -C(=O)-OQ and -OC(=O)-Q (where Q is a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms). Examples of non-fluorinated acrylate monomers include alkyl (meth)acrylates, polyethylene glycol (meth)acrylates, polypropylene glycol (meth)acrylates, methoxypolyethylene glycol (meth)acrylates, and methoxypolypropylene glycol (meth)acrylates. The non-fluorinated acrylate monomer is preferably an alkyl (meth)acrylate. The number of carbon atoms in the alkyl group may be 1 to 30, for example, 6 to 30 (for example, 10 to 30). Specific examples of non-fluorinated acrylate monomers are lauryl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate. Non-fluorinated acrylate polymers can be produced using the same polymerization methods as fluorinated polymers. A saturated or unsaturated hydrocarbon compound is preferably a saturated hydrocarbon. In a saturated or unsaturated hydrocarbon compound, the number of carbon atoms may be 15 or more, preferably 20 to 300, for example, 25 to 100. A specific example of a saturated or unsaturated hydrocarbon compound is paraffin. Silicone compounds are generally used as surface treatment agents (e.g., water repellents). It is preferable that the silicone compound exhibits water-repellent and / or oil-repellent properties. [Amount of each component] (Amount of fluorine-containing polymer) The amount of fluorine-containing polymer (solid content) may be about 0.01 to 60% by weight, preferably about 0.1 to 40% by weight, and more preferably about 5 to 35% by weight, relative to the dispersion. For example, during storage, it may be stored at a high concentration and then diluted to any desired concentration by adding a liquid medium as needed before use. The improved product stability makes it possible to supply high-concentration products, which previously had supply problems due to stability issues. (Amount of unreacted chloride monomers) The concentration of unreacted chloride monomers in the dispersion may be 2.0 ppm or less, 1.5 ppm or less, 1.0 ppm or less, 0.8 ppm or less, 0.5 ppm or less, 0.3 ppm or less, or 0.1 ppm or less. (Amount of liquid medium) The amount of liquid medium may be 30 to 99.9% by weight, particularly 50 to 99% by weight, relative to the dispersion. (Amount of surfactant) In this disclosure, a dispersion of a fluorine-containing polymer, particularly an aqueous dispersion, can be formed even without using a surfactant. The amount of surfactant may be 0.1 to 50 parts by weight, for example, 1 to 30 parts by weight, per 100 parts by weight of the fluorine-containing polymer (or the total of monomers). (Amount of curing agent) The amount of curing agent may be 100 parts by weight or less per 100 parts by weight of fluorine-containing polymer, for example, 0.01 to 30 parts by weight. (Amount of other components) The amount of the non-fluorine water-repellent and / or oil-repellent compound may be 500 parts by weight or less, for example, 5 to 200 parts by weight, particularly 5 to 100 parts by weight, per 100 parts by weight of the fluorine-containing polymer. <Method for producing dispersion> The method for producing the dispersion in this disclosure is: Step (i) involves copolymerizing a fluorine-containing monomer (a) containing a fluoroalkyl group and having a Q value of 2.0 or higher in the Q-e scheme, and a chloride monomer (b) which is at least one selected from vinyl chloride and vinylidene chloride, in a liquid medium to obtain a polymerization solution containing a fluorine-containing polymer, and (ii) A step to reduce the concentration of unreacted chloride monomer (b) in the obtained polymerization solution to 2.0 ppm or less. Includes: [Step (i) to obtain a polymerization solution containing a fluorine-containing polymer] The fluorine-containing polymers in this disclosure can be produced by any conventional polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. In solution polymerization, a method is employed in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, followed by nitrogen purging, and then heating and stirring at a temperature of 30 to 120°C for 30 minutes to 48 hours, for example, 3 to 24 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of monomer. Organic solvents are inert to monomers and dissolve them, and may include, for example, esters (e.g., esters with 2 to 30 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 30 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), and alcohols (e.g., alcohols with 1 to 30 carbon atoms, specifically isopropyl alcohol). Specific examples of organic solvents include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, per 100 parts by weight of the total monomers. In emulsion polymerization, monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and then polymerized by stirring at a temperature of 50 to 80°C for 30 minutes to 48 hours, for example, 3 to 24 hours, after nitrogen purging. Polymerization initiators include water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of monomer. To obtain a polymer dispersion with excellent stability during storage, it is desirable to polymerize the monomers by micronizing them in water using an emulsifying device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. Various emulsifiers, including anionic, cationic, and nonionic types, can be used as emulsifiers, and are used in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely miscible, it is preferable to add a compatibilizer that allows them to be sufficiently miscible, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsification and copolymerization properties. Examples of water-soluble organic solvents include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, and may be used in amounts of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low molecular weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, and may be used in amounts of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers. In polymerization, chain transfer agents may be used. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (e.g., with 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomer. It is preferable to produce the fluorine-containing polymer by emulsion polymerization or solution polymerization. It is preferable to produce a fluorine-containing polymer by polymerization, and then add water (or an aqueous medium) to disperse the fluorine-containing polymer in water. Water (or an aqueous medium) may be added after the fluorine-containing polymer has been produced by polymerization. For example, monomers may be polymerized in the presence of an organic solvent to produce a fluorine-containing polymer, and then water may be added to the polymer mixture, the organic solvent may be removed by distillation, and the fluorine-containing polymer may be dispersed in water. The organic solvent does not need to be removed by distillation. Surfactants may be added before or after polymerization, or they may not be added. An aqueous dispersion can be obtained even if no surfactant is added. Curing agents may be added before or after polymerization, but it is preferable to add them after polymerization. Other components may be added before or after polymerization, or they may not be added. [Chloride monomer removal process (ii)] Examples of methods for removing unreacted vinyl chloride or vinylidene chloride from the polymerization solution after the polymerization reaction include distillation under reduced pressure, distillation by stirring under atmospheric pressure heating, distillation by bubbling of air, nitrogen, or steam under heating or without heating (for example, at 100 cc / min or more, 200 cc / min or more, 300 cc / min or more, or 400 cc / min or more for 3 hours or more, 6 hours or more, 12 hours or more, or 18 hours or more), and methods using packed columns, spin coaters, cylindrical volatilizers, etc. The temperature, time, airflow strength, etc. during the removal process can be changed as appropriate. The chloride monomer (b) may be removed while leaving a portion of the liquid medium in the polymerization solution. <Method of manufacturing the object to be processed> [Processing method] The dispersion of this disclosure can be applied to a workpiece as a surface treatment agent by conventionally known methods. Typically, the dispersion is diluted by dispersing it in an organic solvent or water, and then applied to the surface of the workpiece by known methods such as immersion coating, spray coating, or foam coating, followed by drying. If necessary, it may also be applied together with a suitable crosslinking agent and curing may be performed. Furthermore, it is possible to use the dispersion of this disclosure in combination with insecticides, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixatives, wrinkle inhibitors, etc. The concentration of the polymer in the treatment solution that comes into contact with the textile product may be 0.01 to 10% by weight (especially in the case of immersion coating), for example, 0.05 to 10% by weight. [Object to be processed] Examples of materials to be treated with the surface treatment agents of this disclosure (e.g., water repellents, oil repellents, water- and oil-repellent agents) include textile products, stone materials, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Various examples of textile products can be given. For example, natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Textile products may be in any form, such as fibers or cloth. The dispersion of this disclosure can also be used as an internal or external release agent. The polymer can be applied to a textile product (e.g., cloth) by any known method for treating the textile product with a liquid. The textile product may be immersed in the solution, or the solution may be applied to or sprayed onto the textile product. The treated textile product is preferably dried and cured by heating to exhibit water-repellent and oil-repellent properties. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. Good performance can also be obtained with low-temperature heating (e.g., 100°C to 140°C) in this disclosure. The heating time may be 5 seconds to 60 minutes in this disclosure, for example, 30 seconds to 3 minutes. Alternatively, the polymer may be applied to textile products by cleaning methods, for example, by washing or dry cleaning. The textile products to be treated are typically cloths, including woven fabrics, knitted fabrics and nonwoven fabrics, cloths in the form of clothing and carpets, but may also be fibers or yarns or intermediate textile products (e.g., slivers or rovings). The dispersions of the present disclosure are particularly effective in making textile products (e.g., synthetic fibers) water-repellent and / or oil-repellent. The fibers that make up the textile product may be natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, or inorganic fibers. The fibers may be used individually or in combination of two or more types. Examples of natural fibers include cellulose fibers such as cotton, flax, and wood pulp, as well as chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as ground wood pulp (GP), pressed ground wood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N material), bleached softwood kraft pulp (NBKP; N material, NB material), unbleached hardwood kraft pulp (LUKP; L material), and bleached hardwood kraft pulp (LBKP, L material); and recycled paper pulps such as deinking pulp (DIP) and waste pulp (WP), as well as semi-chemical pulps (CP). Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymerized polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fibers and carbon fibers. Alternatively, the textile product may be leather. The manufacturing polymer may be applied to the leather in the form of an aqueous solution or aqueous emulsion at various stages of leather processing, for example, during the wetting process or during the finishing process, in order to make the leather hydrophobic and oleophobic. Alternatively, the textile product may be paper. The manufacturing polymer may be applied to pre-formed paper, or it may be applied at various stages of papermaking, for example, during the drying period of the paper. "Treatment" means applying the dispersion liquid to the object to be treated by means such as immersion, spraying, coating, etc. By treatment, the polymer which is the active ingredient of the dispersion liquid penetrates into the interior of the object to be treated and / or adheres to the surface of the object to be treated. The embodiments of the present disclosure will be specifically described, but the embodiments do not limit the present disclosure. In the following, % is by weight % unless otherwise specified. The meanings of the abbreviations are as shown in Table 1. [Calculation of Q - e value] The reactivity ratios (r １ , r ２ ) of the fluorine-containing monomer with styrene were determined as follows. For the copolymerization, ethyl acetate (25 g), C8FA and styrene were charged into a 100 ml four-necked flask so that the monomer charging ratio was from 1 / 9 to 9 / 1 (the total molar amount was 0.04 mol). It was heated to 60°C under a nitrogen atmosphere while stirring. Next, 2,2’-bis 2,4-hydroxybutyrate (0.5 mol% of the charged monomers) was added as a polymerization initiator. The copolymerization was carried out so that the monomer conversion rate was 10% or less. For the purification of the copolymer, 10 times the amount of methanol was added to the polymerization solution, and the produced precipitate was centrifuged. It was rewashed with the same volume of methanol and separated in the same manner. The product was filtered. It was dried at 130°C for 1 h. The copolymer composition ratio was determined by F analysis in the produced copolymer. Table 1 shows the monomer charging amounts, the fluorine content in the copolymer, the molar % of FA and the molar % of styrene in the copolymer. From these, f = d[M1] / d[M2], F = [M1] / [M2], F ２ / f, F(f - 1) / f are shown in Table 2. Using the solver function of Microsoft Excel to find the combination of r １ and r ２ such that it becomes the minimum value, the result was r １ = 0.10, r ２ = 0.69. This value r １ = 0.10, r２ = 0.69 and the Q of styrene ２ = 1.0, e ２ Substitute -0.8 into equations [5] and [6] and Q １ = 0.40, e １ = 0.82 was obtained. Similarly, the reactivity ratio of various FA monomers with styrene (r １ ,r ２ The values ​​of Q and e were calculated. The results are shown in Table 3. [Manufacturing Example 1] In a 500 ml poly container, 50 g of fluoroalkyl acrylate (C6FA), 15 g of stearyl acrylate, 3 g of glycidyl methacrylate, 20 g of water-soluble glycol solvent, 294 g of pure water, 2 g of sorbitan fatty acid ester, 2 g of cationic emulsifier, and 6 g of polyoxyethylene alkyl ether were charged. The mixture was heated to 60°C and stirred with a homomixer at 2000 rpm for 1 minute, followed by emulsification and dispersion using ultrasound for 15 minutes. The emulsion dispersion was transferred to a 500 ml autoclave, purged with nitrogen for 15 minutes, and then 0.2 g of lauryl mercaptan and 32 g of vinyl chloride were charged. 1 g of azo group-containing water-soluble initiator was added, and the mixture was heated to 60°C and reacted for 4 hours to obtain an aqueous dispersion of the polymer. The monomer conversion rate by gas chromatography was 99.0–99.8%. This dispersion was further diluted with pure water to prepare an aqueous dispersion with a solid content of 30% by weight. Next, the mixture was heated to 60°C and stirred while bubbling with nitrogen gas at a rate of 500 cc / min for 24 hours to remove unreacted vinyl chloride monomers and obtain an aqueous dispersion containing a fluorine-containing polymer. Gas chromatography analysis revealed no remaining vinyl chloride monomers (detection limit: 1 ppm). Next, vinyl chloride monomers were added to a concentration of 6 ppm to obtain an aqueous dispersion containing a fluorine-containing polymer with a vinyl chloride concentration of 6 ppm. The vinyl chloride concentration was confirmed by gas chromatography analysis. [Manufacturing Examples 2-10] Following the example in Production Example 1, the amount of monomer to be charged and the amount of vinyl chloride monomer to be added later were set as shown in Table 6, and an aqueous dispersion containing a fluorine-containing polymer with a predetermined vinyl chloride concentration was obtained. [Example 1] 33.3 g of an aqueous dispersion containing a fluorine-containing polymer with a solid content of 30% by weight, prepared in Production Example 3, was diluted with tap water to prepare 1000 g of a test solution with a solid content of 1.0%. Polyester fabric and nylon fabric were immersed in this test solution and then squeezed with a mangle. Each fabric was passed through a pin tenter at 160°C for 1 minute to dry and cure. The fabrics treated in this manner were subjected to water repellency and oil repellency tests, Bundesmann tests, and stability evaluation tests using the spray method according to JIS L-1092. The results are shown in Table 6. [Example 2] The aqueous dispersion containing a fluorine-containing polymer with a solid content of 30%, prepared in Production Example 4, was evaluated in accordance with Example 1, using a treatment solution containing a quantitative amount of vinyl chloride monomer. The results are shown in Table 6. [Comparative Examples 1-8] The aqueous dispersions containing fluorine-containing polymers with a solid content of 30%, prepared in Production Examples 1, 2, and 5-10, were treated in the same manner as in Example 1 and evaluated. The results are shown in Table 6. [Water repellency evaluation using the spray method] After storing the treated test fabrics in a constant temperature and humidity chamber at 21°C and 65% humidity for at least 4 hours, the following evaluations were performed. The water repellency of each of the above test fabrics was evaluated according to the spray method of JIS-L-1092 (AATCC-22). Water repellency was evaluated according to the criteria shown in Table 4. A higher score indicates better water repellency. The results are shown in Table 6. [Evaluation of oil repellency] The treated test fabric was stored in a constant temperature and humidity chamber at 21°C and 65% humidity for more than 4 hours, after which the following evaluations were performed. 0.05 ml of the test solution (Table 4) was gently dropped onto the test cloth and left for 30 seconds. If the droplet remained on the test cloth, the test solution was considered to have passed. Oil repellency was evaluated on a 9-point scale from Fail, 1, 2, 3, 4, 5, 6, 7, and 8, with the highest score for the passing test solution being used. The results are shown in Table 6. [Bundesmann Exam] For each of the test fabrics described above, rainfall was induced according to the Bundesmann test described in JIS-L-1092(C) under the conditions of a rainfall rate of 80 cc / min, a rainwater temperature of 20°C, and a rainfall duration of 1 minute, and the amount of water leakage (mL) was measured. The amount of water leakage refers to the amount of water (mL) that passed through the surface of the fabric during the Bundesmann test. The results are shown in Table 6. [Product Stability Testing] After adjusting the solid content concentration to 30% by weight and leaving the dispersion at 50°C for two weeks, the state of the dispersion is visually observed and evaluated according to the following criteria. ◎: No change in appearance ○: No sedimentation is observed, but a very small amount of precipitate is seen on the surface of the dispersion. △: Slight sedimentation is observed, and a very small amount of precipitate is seen on the surface of the dispersion. ×: Separation or sedimentation is observed. Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. The dispersions of this disclosure can be used to impart water-repellent and / or oil-repellent properties to various products.

Claims

DEPCT661. A dispersion consisting of a fluorinated polymer and a liquid medium in which the fluorinated polymer is composed of repeating units derived from fluorinated monomers (a) with a Q value of 2.0 or greater and is composed of at least one fluoroalkyl group and repeating units derived from chloride monomers (b) selected from vinyl chloride and vinylidine chloride, and the dispersion has a concentration of non-reactive chloride monomer (b) of 2.0 parts per million or less.

2. A dispersion according to claim 1 in which the fluorinated monomer (a) It is a compound represented by the formula:CH2=C(-X)-C(=O)-YZ-Rf where X is a halogen atom; Y is -O- or -NH-; Z is a direct bond or a divalent organic group; and Rf is a fluoroalkyl group with 1 to 20 carbon atoms.

3. A dispersion according to claim 2 where X is a chlorine atom.

4. A dispersion according to claim 2 or 3 where Rf is a perfluoroalkyl group with 3 to 6 carbon atoms.

5. Any one of the dispersions according to claims 1 to 4 where the amount of repeat units derived from the chloride monomer (b) is less than 25% by weight compared to the fluorine-containing polymer. 6.A dispersion pursuant to any of the claims 1 to 5 in which the fluorinated polymer is also composed of repeating units derived from a hydrocarbon monomer (c) denoted by the formula:CH2=CA21-C(=O)-O-A22(c), where A21 is a hydrogen atom, a monovalent organic group, or a halogen atom and A22 is a hydrocarbon group with 2 to 40 carbon atoms.

7. A dispersion pursuant to claim 6 in which the fluorinated polymer is also composed of repeating units derived from 8. A dispersion according to claim 6 or 7 where the total amount of repeat units derived from the fluorinated monomer (a), repeat units derived from the chloride monomer (b), and repeat units derived from the hydrocarbon monomer (c) is 90% by weight or more compared to the fluorinated polymer. 9.

10. A dispersion pursuant to any of the claims 1 through 8 in which the fluorinated polymer is also composed of repeat units derived from at least two crosslinkable monomers (d) selected from groups containing reactive groups and olefin double bonds.

10. A dispersion pursuant to claim 9 in which the amount of repeat units derived from fluorinated monomers (a) is 25% by weight or more compared to the fluorinated polymer and the amount of repeat units derived from crosslinkable monomers (d).

11. A dispersion under any of the claims 1 through 10 in which the concentration of the non-reactive chloride monomer (b) is 1.0 parts per million or less.

12. A dispersion under any of the claims 1 through 11 in which the liquid medium contains at least 30% by weight or more of water.

13. A method for producing a dispersion which includes: (i) copolymerization of a fluorine-containing monomer (a) which incorporates a fluoroalkyl group and has a Q value of 2.0 or more in the Q-e scheme and at least one chloride monomer (b) which is selected from vinyl chloride and vinylidine chloride in the liquid medium to obtain a polymerization solution which incorporates a fluorinated polymer and (ii) reducing the concentration of the non-reactive chloride monomer (b) in the resulting polymerization solution to 2.0 parts per million or less.

14. Method for producing a modified item which incorporates the application of one of the dispersions under claims 1 through 12 to the substrate-----------------------------------------------------------;.